Biocide compositions

ABSTRACT

Disclosed are biocide compositions. The compositions are useful in applications relating to the production, transportation, storage, and separation of crude oil and natural gas. Also disclosed are methods of using the compositions, particularly in applications relating to the production, transportation, storage, and separation of crude oil and natural gas.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. continuation patent application which claimspriority to U.S. application Ser. No. 14/448,196 filed Jul. 31, 2014,which claims the benefit of U.S. Provisional Patent Application No.61/861,803, filed Aug. 2, 2013, the entirety of which is hereinincorporated by reference.

FIELD OF THE INVENTION

The present disclosure relates generally to biocides, and moreparticularly to biocides including an imidazoline (e.g., acrylatedimidazoline), a quaternary amine, and a phosphonium compound (e.g.,tetrakis-(hydroxymethyl) phosphonium sulfate).

BACKGROUND OF THE INVENTION

Oilfield systems are subjected to increased risks associated withmicrobial control including: H₂S production, microbial influencedcorrosion (MIC) and biofouling. When MIC is suspected in a system, themain area of concern becomes the biofilm, or sessile organisms, on thesurface of the pipeline. It is widely recognized, within the industry,that in order to be effective at controlling the bacteria within asystem there should be a focus on minimizing biofilm regrowth kineticsfollowing treatment (sessile control) in addition to providingsufficient planktonic kill. While tetrakis-(hydroxymethyl) phosphoniumsulfate, glutaraldehyde, and quaternary ammonium compounds are widelyused as biocides, their efficacy is limited when considering theirability to delay the regrowth kinetics of biofilms after biocidetreatment. Thus, there is an increased need, in the oilfield industry,to provide microbial kill and biofilm control, and in particular, topenetrate and delay the regrowth kinetics of biofilms.

SUMMARY OF THE INVENTION

In one aspect, disclosed is a biocide composition including: animidazoline compound; a quaternary amine; and a phosphonium compound.

The imidazoline compound has formula (I),

-   -   wherein    -   R¹, R⁴, and R⁵ are each independently selected from hydrogen,        alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle,    -   said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle each independently, at each        occurrence, unsubstituted or substituted with 1 to 3        substituents independently selected from halogen, —COR⁶, —CO₂R⁷,        —SO₃R⁸, —PO₃H₂, —CON(R⁹)(R¹⁰), —OR¹¹, and —N(R¹²)(R¹³);    -   R² is a radical derived from a fatty acid;    -   R³ is selected from a radical derived from an unsaturated acid;    -   R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently, at each        occurrence, selected from hydrogen, alkyl, and alkenyl;    -   R¹² and R¹³ are each independently, at each occurrence, selected        from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and        -alkyl-CO₂R¹⁷; and    -   R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are each independently, at each        occurrence, selected from hydrogen, alkyl, and alkenyl.

For compounds of formula (I), R¹ can be unsubstituted C₂-C₆-alkyl; R² is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) ishydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ is hydrogen; and R⁵ ishydrogen.

For compounds of formula (I), R¹ can be linear C₂-alkyl, substitutedwith one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹² ishydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁;R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e)is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ is hydrogen; and R⁵ ishydrogen.

For compounds of formula (I), R¹ can be linear C₂-alkyl, substitutedwith one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹² andR¹³ are each a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷ is hydrogen or is absent;R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e)is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ is hydrogen; and R⁵ ishydrogen.

Further, the imidazoline compound can has formula (II),

-   -   wherein    -   R¹, R⁴, and R⁵ are each independently selected from hydrogen,        alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle,    -   said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle each independently, at each        occurrence, unsubstituted or substituted with 1 to 3        substituents independently selected from halogen, —COR⁶, —CO₂R⁷,        —SO₃R⁸, —PO₃H₂, —CON(R⁹)(R¹⁰), —OR¹¹, and —N(R¹²)(R¹³);    -   R² is a radical derived from a fatty acid;    -   R³ and R^(x) are each independently selected from a radical        derived from an unsaturated acid;    -   R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently, at each        occurrence, selected from hydrogen, alkyl, and alkenyl;    -   R¹² and R¹³ are each independently, at each occurrence, selected        from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and        -alkyl-CO₂R¹⁷; and    -   R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are each independently, at each        occurrence, selected from hydrogen, alkyl, and alkenyl.

For a compound of formula (2), R¹ can be unsubstituted C₂-C₆-alkyl; R²is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) ishydrogen, C₁-C₆-alkyl, or R^(e) is absent; R^(x) is —CH₂CH₂CO₂R^(e),wherein R^(e) is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ ishydrogen; and R⁵ is hydrogen.

For a compound of formula (2), R¹ can be linear C₂-alkyl, substitutedwith one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹² ishydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁;R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e)is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R^(x) is —CH₂CH₂CO₂R^(e),wherein R^(e) is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ ishydrogen; and R⁵ is hydrogen.

For a compound of formula (2), R¹ can be linear C₂-alkyl, substitutedwith one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹² andR¹³ are each a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷ is hydrogen or is absent;R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e)is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R^(x) is —CH₂CH₂CO₂R^(e),wherein R^(e) is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ ishydrogen; and R⁵ is hydrogen.

Additionally, the imidazoline compound can have a structure of formula(III),

-   -   wherein    -   R¹, R⁴, and R⁵ are each independently selected from hydrogen,        alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle,    -   said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle each independently, at each        occurrence, unsubstituted or substituted with 1 to 3        substituents independently selected from halogen, —COR⁶, —CO₂R⁷,        —SO₃R⁸, —PO₃H₂, —CON(R⁹)(R¹⁰), —OR¹¹, and —N(R¹²)(R¹³);    -   R² is a radical derived from a fatty acid;

1R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently, at eachoccurrence, selected from hydrogen, alkyl, and alkenyl;

-   -   R¹² and R¹³ are each independently, at each occurrence, selected        from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and        -alkyl-CO₂R¹⁷; and    -   R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are each independently, at each        occurrence, selected from hydrogen, alkyl, and alkenyl.

For compounds of formula (3), R¹ can be unsubstituted C₂-C₆-alkyl; R² is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ is hydrogen; and R⁵ is hydrogen.

For a compound of formula (3), R¹ can be linear C₂-alkyl, substitutedwith one substituent that is a terminal —N(R¹²)(R¹³), wherein R¹² ishydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁;R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ is hydrogen; and R⁵ is hydrogen.

For a compound of formula (3), R¹ is linear C₂-alkyl, substituted withone substituent that is a terminal —N(R¹²)(R¹³), wherein R¹² and R¹³ areeach a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷ is hydrogen or is absent; R² is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ is hydrogen; and R⁵ is hydrogen.

The quaternary amine can have the formula[N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻]

-   -   wherein    -   R^(5a), R^(6a), R^(7a), and R^(8a) are each independently        selected from substituted or unsubstituted C₁-C₁₈-alkyl; and    -   X is Cl, Br or I.

For the quaternary amine, R^(5a), R^(6a), R^(7a), and R^(8a) can eachindependently be selected from the group consisting of unsubstitutedC₁-C₁₈-alkyl, C₁-C₁₈-hydroxyalkyl, and benzyl.

The quaternary amine can be selected from the group consisting oftetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropylammonium chloride, tetrabutyl ammonium chloride, tetrahexyl ammoniumchloride, tetraoctyl ammonium chloride, benzyltrimethyl ammoniumchloride, benzyltriethyl ammonium chloride, phenyltrimethyl ammoniumchloride, phenyltriethyl ammonium chloride, cetyl benzyldimethylammonium chloride, hexadecyl trimethyl ammonium chloride, dimethylC₁₂-₁₆-alkyl benzyl ammonium chloride, monomethyl di-C₁₂-₁₆-alkyl benzylquaternary ammonium chloride, benzyl triethanolamine quaternary ammoniumchloride, benzyl dimethylaminoethanolamine quaternary ammonium chloride,cocoalkyl dimethyl benzyl ammonium chloride, and combinations thereof.

The phosphonium compound can be selected from the group consisting ofalkyltris(hydroxyorgano)phosphonium salts,alkenyltris(hydroxyorgano)phosphonium salts,tetrakis(hydroxyorgano)phosphonium salts, and combinations thereof.

Further, the phosphonium compound can be selected from the groupconsisting of C₁-C₃-alkyltris(hydroxymethyl)phosphonium salts,C₂-C₃-alkenyltris(hydroxymethyl)phosphonium salts,tetrakis(hydroxymethyl)phosphonium salts, and combinations thereof.

Additionally, the phosphonium compound can be selected from the groupconsisting of tetrakis(hydroxymethyl)phosphonium sulphate (THPS),tetrakis(hydroxymethyl)phosphonium chloride,tetrakis(hydroxymethyl)phosphonium phosphate,tetrakis(hydroxymethyl)phosphonium formate,tetrakis(hydroxymethyl)phosphonium acetate,tetrakis(hydroxymethyl)phosphonium oxalate, and combinations thereof.

The composition can further include a demulsifier. The demulsifier canbe selected from the group consisting of dodecylbenzylsulfonic acid(DDBSA), the sodium salt of xylenesulfonic acid (NAXSA), epoxylated andpropoxylated compounds, anionic cationic and nonionic surfactants, andresins, phenolic and epoxide resins, and combinations thereof.

The composition can further comprise one or more additional components,each component independently selected from the group consisting ofcorrosion inhibitors, solvents, asphaltene inhibitors, paraffininhibitors, scale inhibitors, emulsifiers, water clarifiers,dispersants, gas hydrate inhibitors, biocides, pH modifiers, andsurfactants.

In another aspect, disclosed is a method of controlling biofouling, themethod comprising providing an effective amount of a composition of theinvention into a system. The method can include controlling microbeproliferation in a system used in the production, transportation,storage, and separation of crude oil and natural gas. The method caninclude controlling microbe proliferation in a system used in acoal-fired process, a waste-water process, a farm, a slaughter house, aland-fill, a municipality waste-water plant, a coking coal process, or abiofuel process.

The compounds, compositions, methods and processes are further describedherein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts biocidal activity of compositions including a quaternaryamine and an imidazoline.

FIG. 2 depicts biocidal activity of compositions including one or moreof an imidazoline, a quaternary amine, and a phosphonium salt.

FIG. 3 depicts biocidal activity of compositions including varyingratios of imidazoline, quaternary amine, and phosphonium saltcomponents.

FIG. 4 depicts an emulsion tendency study.

FIGS. 5A, 5B, and 5C depict graphs of corrosion rate versusconcentration for V08, THPS, and glutaraldehyde.

DETAILED DESCRIPTION

Disclosed herein are biocide compositions, methods of using saidcompositions, and processes for their preparation. The compositionsinclude a synergistic combination of at least one imidazoline compound,at least one quaternary amine, and at least one phosphonium compound.The compositions can further include an emulsion breaker to facilitateoil/water separation in the system being treated.

The compositions are particularly useful for controlling microbeproliferation in equipment used in the production, transportation,storage, and separation of crude oil and natural gas. The compositionskill planktonic and sessile microorganisms and provide enhanced controlof biofilm kinetic regrowth (sessile control). The compositions areeffective against common oilfield microbes (e.g., sulfate reducing andacid producing bacteria), including genera such as Desulfovibrio,Desulfomicrobium, Shewanella, Clostridium, and Pseudomonas, amongstothers. The compositions thus reduce the required biocide treatment rateand treatment frequency compared to biocides currently on the market.

1. Definition of Terms

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety. The materials, methods, and examples disclosed herein areillustrative only and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a,” “and” and “the” include plural references unless the contextclearly dictates otherwise. The present disclosure also contemplatesother embodiments “comprising,” “consisting of” and “consistingessentially of,” the embodiments or elements presented herein, whetherexplicitly set forth or not.

The term “suitable substituent,” as used herein, is intended to mean achemically acceptable functional group, preferably a moiety that doesnot negate the activity of the inventive compounds. Such suitablesubstituents include, but are not limited to halo groups, perfluoroalkylgroups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynylgroups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups,alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxygroups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxygroups, HO—(C═O)— groups, heterocylic groups, cycloalkyl groups, aminogroups, alkyl- and dialkylamino groups, carbamoyl groups, alkylcarbonylgroups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups,alkylsulfonyl groups, and arylsulfonyl groups. Those skilled in the artwill appreciate that many substituents can be substituted by additionalsubstituents.

The term “alkyl,” as used herein, refers to a linear or branchedhydrocarbon radical, preferably having 1 to 32 carbon atoms (i.e., 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons). Alkyl groupsinclude, but are not limited to, methyl, ethyl, n-propyl, isopropyl,n-butyl, iso-butyl, secondary-butyl, and tertiary-butyl. Alkyl groupscan be unsubstituted or substituted by one or more suitablesubstituents, as defined above.

The term “alkenyl,” as used herein, refers to a straight or branchedhydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39,30, 31, or 32 carbons, and having one or more carbon-carbon doublebonds. Alkenyl groups include, but are not limited to, ethenyl,1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl-1-propenyl,1-butenyl, and 2-butenyl. Alkenyl groups can be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkynyl,” as used herein, refers to a straight or branchedhydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39,30, 31, or 32 carbons, and having one or more carbon-carbon triplebonds. Alkynyl groups include, but are not limited to, ethynyl,propynyl, and butynyl. Alkynyl groups can be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkoxy,” as used herein, refers to an alkyl group, as definedherein, appended to the parent molecular moiety through an oxygen atom.

The term “aryl,” as used herein, means monocyclic, bicyclic, ortricyclic aromatic radicals such as phenyl, naphthyl,tetrahydronaphthyl, indanyl and the like; optionally substituted by oneor more suitable substituents, preferably 1 to 5 suitable substituents,as defined above.

The term “arylalkyl,” as used herein, refers to an aryl group attachedto the parent molecular moiety through an alkyl group. Arylalkyl groupscan be unsubstituted or substituted by one or more suitablesubstituents, as defined above.

The term “alkylarylalkyl,” as used herein, refers to an alkylaryl groupattached to the parent molecular moiety through an alkyl group.Alkylarylalkyl groups can be unsubstituted or substituted by one or moresuitable substituents, as defined above.

The term “carbonyl,” “(C═O),” or “—C(O)—” (as used in phrases such asalkylcarbonyl, alkyl —(C═O)— or alkoxycarbonyl) refers to the joinder ofthe >C═O moiety to a second moiety such as an alkyl or amino group (i.e.an amido group). Alkoxycarbonylamino (i.e. alkoxy(C═O)—NH—) refers to analkyl carbamate group. The carbonyl group is also equivalently definedherein as (C═O). Alkylcarbonylamino refers to groups such as acetamide.

The term “cycloalkyl,” as used herein, refers to a mono, bicyclic ortricyclic carbocyclic radical (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclopentenyl, cyclohexenyl, bicyclo[2.2.1]heptanyl,bicyclo[3.2.1]octanyl and bicyclo[5.2.0]nonanyl, etc.); optionallycontaining 1 or 2 double bonds. Cycloalkyl groups can be unsubstitutedor substituted by one or more suitable substituents, preferably 1 to 5suitable substituents, as defined above.

The term “cycloalkylalkyl,” as used herein, refers to a cycloalkyl groupattached to the parent molecular moiety through an alkyl group.Cycloalkylalkyl groups can be unsubstituted or substituted by one ormore suitable substituents, as defined above.

The term “alkylcycloalkylalkyl,” as used herein, refers to acycloalkylalkyl group substituted by one or more alkyl groups.Alkylcycloalkylalkyl groups can be unsubstituted or substituted by oneor more suitable substituents, as defined above.

The term “halo” or “halogen,” as used herein, refers to a fluoro,chloro, bromo or iodo radical.

The term “heteroaryl,” as used herein, refers to a monocyclic, bicyclic,or tricyclic aromatic heterocyclic group containing one or moreheteroatoms (e.g., 1 to 3 heteroatoms) selected from O, S and N in thering(s). Heteroaryl groups include, but are not limited to, pyridyl,pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, imidazolyl,pyrrolyl, oxazolyl (e.g., 1,3-oxazolyl, 1,2-oxazolyl), thiazolyl (e.g.,1,2-thiazolyl, 1,3-thiazolyl), pyrazolyl, tetrazolyl, triazolyl (e.g.,1,2,3-triazolyl, 1,2,4-triazolyl), oxadiazolyl (e.g.,1,2,3-oxadiazolyl), thiadiazolyl (e.g., 1,3,4-thiadiazolyl), quinolyl,isoquinolyl, benzothienyl, benzofuryl, and indolyl. Heteroaryl groupscan be unsubstituted or substituted by one or more suitablesubstituents, preferably 1 to 5 suitable substituents, as defined above.

The term “heteroarylalkyl,” as used herein, refers to a heteroaryl groupattached to the parent molecular moiety through an alkyl group.Heteroarylalkyl groups can be unsubstituted or substituted by one ormore suitable substituents, as defined above.

The term “alkylheteroarylalkyl,” as used herein, refers to aheteroarylalkyl group substituted by one or more alkyl groups.Alkylheteroarylalkyl groups can be unsubstituted or substituted by oneor more suitable substituents, as defined above.

The term “heterocycle” or “heterocyclyl,” as used herein, refers to amonocyclic, bicyclic, or tricyclic group containing 1 to 4 heteroatomsselected from N, O, S(O)_(n), P(O)_(n), PR^(z), NH or NR^(z), whereinR^(z) is a suitable substituent. Heterocyclic groups optionally contain1 or 2 double bonds. Heterocyclic groups include, but are not limitedto, azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl,piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl,thiomorpholinyl, tetrahydrothiazinyl, tetrahydro-thiadiazinyl,morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl,indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, andbenzoxazinyl. Examples of monocyclic saturated or partially saturatedring systems are tetrahydrofuran-2-yl, tetrahydrofuran-3-yl,imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl,pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl,piperidin-2-yl, piperidin-3-yl, piperazin-1-yl, piperazin-2-yl,piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine,1,3-thiazolidin-3-yl, 1,2-pyrazolidin-2-yl, 1,3-pyrazolidin-1-yl,thiomorpholin-yl, 1,2-tetrahydrothiazin-2-yl,1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazin-yl, morpholin-yl,1,2-tetrahydrodiazin-2-yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-2-yl,and 1,2,5-oxathiazin-4-yl. Heterocyclic groups can be unsubstituted orsubstituted by one or more suitable substituents, preferably 1 to 3suitable substituents, as defined above.

The term “heterocyclylalkyl,” as used herein, refers to a heterocyclegroup attached to the parent molecular moiety through an alkyl group.Heterocyclylalkyl groups can be unsubstituted or substituted by one ormore suitable substituents, as defined above.

The term “alkylheterocyclylalkyl,” as used herein refers to aheterocyclylalkyl group substituted by one or more alkyl groups.Alkylheterocyclylalkyl groups can be unsubstituted or substituted by oneor more suitable substituents, as defined above.

The term “hydroxy,” as used herein, refers to an —OH group.

The term “oxo,” as used herein, refers to a double bonded oxygen (═O)radical wherein the bond partner is a carbon atom. Such a radical canalso be thought as a carbonyl group.

The term “acrylate,” as used herein, refers to the material resultingfrom the Michael addition of acrylic acid to an imidazoline. Theaddition of this chemical moiety to the imidazoline increases its watersolubility, enabling it to reach metal surfaces which are submergedbeneath an aqueous layer.

The term “TOFA,” as used herein, refers to a tall oil fatty acid that isa distilled product derived from trees and includes a mixture of fattyacids, C₁₇H₃₁₋₃₅ COOH with a CAS No. 61790-12-3. It is a mixture ofoleic acid as a major component, linoleic acid and saturated fatty acids(e.g., about 46% oleic acid, about 41% linoleic acid, about 4% stearicacid, and about 9% other acids).

The term “decyl”, as used herein, means a —C₁₀H₂₁ alkyl radical, alsoreferred to as “capryl”.

The term “dodecyl”, as used herein, means a —C₁₂H₂₅ alkyl radical, alsoreferred to as “lauryl”.

The term “hexadecyl”, as used herein, means a —C₁₆H₃₃ alkyl radical,also referred to as “palmityl”.

The term “hexyl”, as used herein, means a —C₆H₁₃ alkyl radical, alsoreferred to as “caproyl”.

The term “octadecadienyl”, as used herein, means acis,cis-9,12-octadecadienyl radical, also referred to as “linoleyl”.

The term “octadecenyl”, as used herein, means a cis-9-octadecenylradical, also referred to as “oleyl”.

The term “octadecyl”, as used herein, means a —C₁₈H₃₇ alkyl radical,also referred to as “stearyl”.

The term “octyl”, as used herein, means a —C₈H₁₇ alkyl radical, alsoreferred to as “caprylyl.”

The term “tetradecyl”, as used herein, means a —C₁₄H₂₉ alkyl radical,also referred to as “myristyl”.

The term “myristoleic acid” or “(Z)-tetradec-9-enoic acid,” as usedherein, refers to

The term “palmitoleic acid” or “(Z)-hexadec-9-enoic acid,” as usedherein, refers to

The term “sapienic acid” or “(Z)-hexadec-6-enoic acid,” as used herein,refers to

The term “oleic acid” or “(Z)-octadec-9-enoic acid,” as used herein,refers to

The term “elaidic acid” or “(E)-octadec-9-enoic acid,” as used herein,refers to

The term “vaccenic acid” or “(E)-octadec-11-enoic acid,” as used herein,refers to

The term “linoleic acid” or “(9Z,12Z)-octadeca-9,12-dienoic acid,” asused herein, refers to

The term “linoelaidic acid” or “(9E,12E)-octadeca-9,12-dienoic acid,” asused herein, refers to

The term “α-linolenic acid” or “(9Z,12Z,15Z)-octadeca-9,12,15-trienoicacid,” as used herein, refers to

The term “arachidonic acid” or“(5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid,” as used herein,refers to

The term “eicosapentaenoic acid” or“(5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoic acid,” as usedherein, refers to

The term “erucic acid” or “(Z)-docos-13-enoic acid,” as used herein,refers to

The term “docosahexaenoic acid” or“(4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoic acid,” as usedherein, refers to

The term “hexadecatrienoic acid” or“(7Z,10Z,13Z)-hexadeca-7,10,13-trienoic acid,” as used herein, refers to

The term “stearidonic acid” or“(6Z,9Z,12Z,15Z)-octadeca-6,9,12,15-tetraenoic acid,” as used herein,refers to

The term “eicosatrienoic acid” or “(11Z,14Z,17Z)-icosa-11,14,17-trienoicacid,” as used herein, refers to

The term “eicosatetraenoic acid” or“(5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoic acid,” as usedherein, refers to

The term “heneicosapentaenoic acid” or“(6Z,9Z,12Z,15Z,18Z)-henicosa-6,9,12,15,18-pentaenoic acid,” as usedherein, refers to

The term “clupanodonic acid” or“(7Z,10Z,13Z,16Z,19Z)-docosa-7,10,13,16,19-pentaenoic acid,” as usedherein, refers to

The term “osbond acid” or “(4Z,7Z,10Z,13Z,16Z)-docosa-4,7,10,13,16-pentaenoic acid,” as used herein, refersto

The term “(9Z,12Z,15Z,18Z,21Z)-tetracosa-9,12,15,18,21-pentaenoic acid,”as used herein refers to

The term “nisinic acid” or“(6Z,9Z,12Z,15Z,18Z,21Z)-tetracosa-6,9,12,15,18,21-hexaenoic acid,” asused herein, refers to

The term “γ-linolenic acid” or “(6Z,9Z,12Z)-octadeca-6,9,12-trienoicacid,” as used herein, refers to

The term “eicosadienoic acid” or “(11Z,14Z)-icosa-11,14-dienoic acid,”as used herein, refers to

The term “dihomo-γ-linolenic acid” or“(8Z,11Z,14Z)-icosa-8,11,14-trienoic acid,” as used herein, refers to

The term “docosadienoic acid” or “(13Z,16Z)-docosa-13,16-dienoic acid,”as used herein, refers to

The term “adrenic acid” or“(7Z,10Z,13Z,16Z)-docosa-7,10,13,16-tetraenoic acid,” as used herein,refers to

The term “tetracosatetraenoic acid” or“(9Z,12Z,15Z,18Z)-tetracosa-9,12,15,18-tetraenoic acid,” as used herein,refers to

The term “(6Z,9Z,12Z,15Z,18Z)-tetracosa-6,9,12,15,18-pentaenoic acid,”as used herein, refers to

The term “(Z)-Eicos-11-enoic acid” or “(Z)-icos-11-enoic acid,” as usedherein, refers to

The term “paullinic acid” or “(Z)-icos-13-enoic acid,” as used herein,refers to

The term “mead acid” or “(5Z,8Z,11Z)-Eicosa-5,8,11-trienoic acid,” asused herein, refers to

The term “nervonic acid,” or “(Z)-tetracos-15-enoic acid,” as usedherein, refers to

The term “rumenic acid” or “(9Z,11E)-octadeca-9,11-dienoic acid,” asused herein, refers to

The term “α-calendic acid” or “(8E,10E,12Z)-octadeca-8,10,12-trienoicacid,” as used herein, refers to

The term “β-calendic acid” or “(8E,10E,12E)-octadeca-8,10,12-trienoicacid,” as used herein, refers to

The term “jacaric acid” or “(8E,10Z,12E)-octadeca-8,10,12-trienoicacid,”

The term “α-eleostearic acid” or “(9Z,11E,13E)-octadeca-9,11,13-trienoicacid,” as used herein, refers to

The term “β-eleostearic acid” or “(9E,11E,13E)-octadeca-9,11,13-trienoicacid,” as used herein, refers to

The term “catalpic acid” or “(9E,11E,13Z)-octadeca-9,11,13-trienoicacid,” as used herein, refers to

The term “punicic acid” or “(9Z,11E,13Z)-octadeca-9,11,13-trienoicacid,” as used herein, refers to

The term “rumelenic acid” or “(9E,11Z,15E)-octadeca-9,11,15-trienoicacid,” as used herein, refers to

The term “α-parinaric acid” or“(9Z,11E,13E,15Z)-octadeca-9,11,13,15-tetraenoic acid,” as used herein,refers to

The term “β-parinaric acid” or“(9E,11E,13E,15E)-octadeca-9,11,13,15-tetraenoic acid,” as used herein,refers to

The term “bosseopentaenoic acid” or“(5Z,8Z,10E,12E,14Z)-icosa-5,8,10,12,14-pentaenoic acid,” as usedherein, refers to

The term “pinolenic acid” or “(5Z,9Z,12Z)-octadeca-5,9,12-trienoicacid,” as used herein, refers to

The term “podocarpic acid” or “(5Z,11Z,14Z)-icosa-5,11,14-trienoicacid,” as used herein, refers to

The term “propionic acid,” as used herein, refers to CH₃CH₂COOH.

The term “butyric acid,” as used herein, refers to CH₃(CH₂)₂COOH.

The term “valeric acid,” as used herein, refers to CH₃(CH₂)₃COOH.

The term “caproic acid,” as used herein, refers to CH₃(CH₂)₄COOH.

The term “enanthic acid,” as used herein, refers to CH₃(CH₂)₅COOH.

The term “caprylic acid,” as used herein, refers to CH₃(CH₂)₆COOH.

The term “pelargonic acid,” as used herein, refers to CH₃(CH₂)₇COOH.

The term “capric acid,” as used herein, refers to CH₃(CH₂)₈COOH.

The term “undecylic acid,” as used herein, refers to CH₃(CH₂)₉COOH.

The term “lauric acid,” as used herein, refers to CH₃(CH₂)₁₀COOH.

The term “tridecylic acid,” as used herein, refers to CH₃(CH₂)₁₁COOH.

The term “myristic acid,” as used herein, refers to CH₃(CH₂)₁₂COOH.

The term “pentadecylic acid,” as used herein, refers to CH₃(CH₂)₁₃COOH.

The term “palmitic acid,” as used herein, refers to CH₃(CH₂)₁₄COOH.

The term “margaric acid,” as used herein, refers to CH₃(CH₂)₁₅COOH.

The term “stearic acid,” as used herein, refers to CH₃(CH₂)₁₆COOH.

The term “nonadecylic acid,” as used herein, refers to CH₃(CH₂)₁₇COOH.

The term “arachidic acid,” as used herein, refers to CH₃(CH₂)₁₈COOH.

The term “heneicosylic acid,” as used herein, refers to CH₃(CH₂)₁₉COOH.

The term “behenic acid,” as used herein, refers to CH₃(CH₂)₂₀COOH.

The term “tricosylic acid,” as used herein, refers to CH₃(CH₂)₂₁COOH.

The term “lignoceric acid,” as used herein, refers to CH₃(CH₂)₂₂COOH.

The term “pentacosylic acid,” as used herein, refers to CH₃(CH₂)₂₃COOH.

The term “cerotic acid,” as used herein, refers to CH₃(CH₂)₂₄COOH.

The term “heptacosylic acid,” as used herein, refers to CH₃(CH₂)₂₅COOH.

The term “montanic acid,” as used herein, refers to CH₃(CH₂)₂₆COOH.

The term “nonacosylic acid,” as used herein, refers to CH₃(CH₂)₂₇COOH.

The term “melissic acid,” as used herein, refers to CH₃(CH₂)₂₈COOH.

The term “henatriacontylic acid,” as used herein, refers toCH₃(CH₂)₂₉COOH.

The term “lacceroic acid,” as used herein, refers to CH₃(CH₂)₃₀COOH.

The term “psyllic acid,” as used herein, refers to CH₃(CH₂)₃₁COOH.

The term “geddic acid,” as used herein, refers to CH₃(CH₂)₃₂COOH.

The term “ceroplastic acid,” as used herein, refers to CH₃(CH₂)₃₃COOH.

The term “hexatriacontylic acid,” as used herein, refers toCH₃(CH₂)₃₄COOH.

2. Compositions

The compositions disclosed herein include an imidazoline compound, aquaternary amine, and a phosphonium compound. The compositions canfurther include a demulsifer. The compositions can further include asynergist. The compositions can further include a solvent. Thecompositions can further include one or more additional components.

The composition can include an imidazoline compound, a quaternary amine,a phosphonium compound, and a demulsifier.

Further, the composition can include an imidazoline compound, aquaternary amine, a phosphonium compound, a demulsifier, and asynergist.

Additionally, the composition can include an imidazoline compound, aquaternary amine, a phosphonium compound, a demulsifier, and a solvent.

Yet further, the composition can include an imidazoline compound, aquaternary amine, a phosphonium compound, and a solvent.

Additionally, the composition can include an imidazoline compound, aquaternary amine, a phosphonium compound, a synergist, and a solvent.

Further, the composition can include an imidazoline compound, aquaternary amine, a phosphonium compound, a demulsifier, a synergist,and a solvent.

a. Imidazoline Compounds

The compositions disclosed herein include at least one imidazolinecompound. The imidazoline compound can have formula (I), (II), or (III),

-   -   wherein    -   R¹, R⁴, and R⁵ are each independently selected from hydrogen,        alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle,    -   said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl,        heteroaryl, and heterocycle each independently, at each        occurrence, unsubstituted or substituted with 1 to 3        substituents independently selected from halogen, —COR⁶, —CO₂R⁷,        —SO₃R⁸, —PO₃H₂, —CON(R⁹)(R¹⁰), —OR¹¹, and —N(R¹²)(R¹³);    -   R² is a radical derived from a fatty acid;    -   R³ and R^(x) are each independently selected from a radical        derived from an unsaturated acid;    -   R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently, at each        occurrence, selected from hydrogen, alkyl, and alkenyl;    -   R¹² and R¹³ are each independently, at each occurrence, selected        from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and        -alkyl-CO₂R¹⁷; and    -   R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are each independently, at each        occurrence, selected from hydrogen, alkyl, and alkenyl.

For these imidazolines, R groups of carboxylic acid moieties can beabsent where the R═H and the carboxylic acid moiety is deprotonated. Forexample, R¹⁵ and/or R¹⁷ can be absent where the R¹² and/or R¹³ is adeprotonated carboxylic acid moiety (e.g., where R¹² is —CH₂CH₂CO₂ ³¹ ).

For an imidazoline compound, R¹ can be unsubstituted alkyl. For example,R¹ can be unsubstituted C₁-C₁₀-alkyl (e.g., methyl, ethyl, propyl (e.g.,n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, tert-butyl,sec-butyl), pentyl (e.g., n-pentyl, isopentyl, tert-pentyl, neopentyl,sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl, or decyl). Further,R¹ can be unsubstituted C₂-C₁₀-alkyl. For these imidazoline compounds,R¹ can be unsubstituted C₂-C₅-alkyl. Further, R¹ can be unsubstitutedC₂-C₆-alkyl. Preferably, R¹ is propyl, butyl, or hexyl.

For these imidazolines, R¹ is substituted alkyl. For example, R¹ issubstituted C₁-C₁₀-alkyl, substituted C₂-C₁₀-alkyl, substitutedC₂-C₅-alkyl, or substituted C₂-C₆-alkyl. Further, R¹ is C₁-C₁₀-alkyl,C₂-C₁₀-alkyl, C₂-C₈-alkyl, or C₂-C₆-alkyl, substituted with onesubstituent selected from —COR⁶, —CO₂R⁷, —SO₃R⁸, —PO₃H₂, —CON(R⁹)(R¹⁰),—OR¹¹, and —N(R¹²)(R¹³), wherein R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³are as defined above. More specifically, R¹ is C₂-C₆-alkyl, substitutedwith one substituent selected from —N(R¹²)(R¹³), wherein R¹² and R¹³ areeach independently selected from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵,-alkyl-COR¹⁶, and -alkyl-CO₂R¹⁷, wherein R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are asdefined above. Further, R¹ is C₂-C₆-alkyl, substituted with onesubstituent selected from —N(R¹²)(R¹³), wherein R¹² and R¹³ are eachindependently selected from hydrogen, C₂-C₆-alkyl, —COR¹⁴, —CO₂R¹⁵,—C₂-C₆-alkyl-COR¹⁶, and —C₂-C₆-alkyl-CO₂R¹⁷, wherein R¹⁴, R¹⁵, R¹⁶, andR¹⁷ are selected from hydrogen and C₁-C₃₄-alkyl. For these imidazolines,R¹ is linear C₂-C₆-alkyl, substituted with one substituent that is aterminal —N(R¹²)(R¹³), wherein R¹² and R¹³ are each independentlyselected from hydrogen, —COR¹⁴, —CO₂R¹⁵, —C₂-C₆-alkyl-COR¹⁶, and—C₂-C₆-alkyl-CO₂R¹⁷, wherein R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are selected fromhydrogen and C₁-C₃₄-alkyl. For example, R¹ is linear C₂-alkyl,substituted with one substituent that is a terminal —N(R¹²)(R¹³),wherein R¹² is hydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is —C₁₇H₃₅,—C₁₇H₃₃, or —C₁₇H₃₁. Further, R¹ is linear C₂-alkyl, substituted withone substituent that is a terminal —N(R¹²)(R¹³), wherein R¹² and R¹³ areeach a —C₂-alkyl -CO₂R¹⁷, wherein R¹⁷ is hydrogen.

For the imidazolines of formulae (I), (II), and (III), R² isC₄-C₃₄-alkyl or C₄-C₃₄-alkenyl. For example, R² is —(CH₂)₃CH₃;—(CH₂)₄CH₃; —(CH₂)₅CH₃; —(CH₂)₆CH₃; —(CH₂)₇CH₃; —(CH₂)₈CH₃; —(CH₂)₉CH₃;—(CH₂)₁₀CH₃; —(CH₂)₁₁CH₃; —(CH₂)₁₂CH₃; —(CH₂)₁₃CH₃; —(CH₂)₁₄CH₃;—(CH₂)₁₅CH₃; —(CH₂)₁₆CH₃; —(CH₂)₁₇CH₃; —(CH₂)₁₈CH₃; —(CH₂)₁₉CH₃;—(CH₂)₂₀CH₃; —(CH₂)₂₁CH₃; —(CH₂)₂₂CH₃; —(CH₂)₂₃CH₃; —(CH₂)₂₄CH₃;—(CH₂)₂₅CH₃; —(CH₂)₂₆CH₃; —(CH₂)₂₇CH₃; —(CH₂)₂₈CH₃; —(CH₂)₂₉CH₃;—(CH₂)₃₀CH₃; —(CH₂)₃₁CH₃; —(CH₂)₃₂CH₃; —(CH₂)₃₃CH₃; —(CH₂)₃₄CH₃;—(CH₂)₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₃CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₇CH₃;—(CH₂)₃CH═CHCH₂CH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₃CH═CH(CH₂)₄CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₃CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₃CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₃CH═CHCH═CHCH═CHCH═CHCH═CH(CH₂)₄CH₃; —(CH₂)₄CH═CH(CH₂)₈CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₅CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₅CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₅CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₆CH═CHCH═CHCH═CH(CH₂)₄CH₃;—(CH₂)₆CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃; —(CH₂)₇CH═CH(CH₂)₃CH₃;—(CH₂)₇CH═CH(CH₂)₅CH₃; —(CH₂)₇CH═CH(CH₂)₇CH₃;—(CH₂)₇CH═CHCH═CHCH═CH(CH₂)₃CH₃; —(CH₂)₇CH═CHCH═CH(CH₂)₅CH₃;—(CH₂)₇CH═CHCH₂CH═CH(CH₂)₄CH₃; —(CH₂)₇CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₇CH═CHCH═CHCH₂CH₂CH═CHCH₂CH₃; —(CH₂)₇CH═CHCH═CHCH═CHCH═CHCH₂CH₃;—(CH₂)₇CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₇CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₇CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₉CH═CH(CH₂)₅CH₃; —(CH₂)₉CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₉CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃; —(CH₂)₉CH═CH(CH₂)₇CH₃;—(CH₂)₁₁CH═CH(CH₂)₅CH₃; —(CH₂)₁₁CH═CH(CH₂)₇CH₃;—(CH₂)₁₁CH═CHCH₂CH═CH(CH₂)₄CH₃; or —(CH₂)₁₃CH═CH(CH₂)₇CH₃.

For the imidazolines, R² can be a radical derived from a saturated orunsaturated fatty acid. Suitable saturated fatty acids include, but arenot limited to, butyric acid, valeric acid, caproic acid, enanthic acid,caprylic acid, pelargonic acid, capric acid, undecylic acid, lauricacid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid,margaric acid, stearic acid, nonadecylic acid, arachidic acid,heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid,pentacosylic acid, cerotic acid, heptacosylic acid, montanic acid,nonacosylic acid, melissic acid, henatriacontylic acid, lacceroic acid,psyllic acid, geddic acid, ceroplastic acid, and hexatriacontylic acid.Suitable unsaturated fatty acids include, but are not limited to,myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidicacid, vaccenic acid, linoleic acid, linoelaidic acid, α-linolenic acid,arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoicacid, hexadecatrienoic acid, stearidonic acid, eicosatrienoic acid,eicosatetraenoic acid, heneicosapentaenoic acid, clupanodonic acid,osbond acid, (9Z,12Z,15Z,18Z,21Z)-tetracosa-9,12,15,18,21-pentaenoicacid, nisinic acid, γ-linolenic acid, eicosadienoic acid,dihomo-γ-linolenic acid, docosadienoic acid, adrenic acid,tetracosatetraenoic acid,(6Z,9Z,12Z,15Z,18Z)-tetracosa-6,9,12,15,18-pentaenoic acid,(Z)-Eicos-11-enoic acid, mead acid, erucic acid, nervonic acid, rumenicacid, α-calendic acid, β-calendic acid, jacaric acid, α-eleostearicacid, β-eleostearic acid, catalpic acid, punicic acid, rumelenic acid,α-parinaric acid, β-parinaric acid, bosseopentaenoic acid, pinolenicacid, and podocarpic acid. Preferably, R² is derived from coconut oil,beef tallow, or tall oil fatty acids (TOFA).

For the imidazoline, R³ is —C(R^(a)R^(b))—C(R^(c)R^(d))—CO₂R^(e),wherein R^(a), R^(b), R^(c), and R^(d) are each independently selectedfrom the group consisting of hydrogen (—H), halogen, and alkyl, andwherein R^(e) is hydrogen (—H) or alkyl. For example, R³ is—C(R^(a)R^(b))—C(R^(c)R^(d))—CO₂R^(e), wherein R^(a), R^(b), R^(c), andR^(d) are each independently selected from the group consisting ofhydrogen (—H), halogen, and C₁-C₆-alkyl, and wherein R^(e) is hydrogen(—H) or C₁-C₆-alkyl. Further, R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) ishydrogen (—H) or C₁-C₆-alkyl. Additionally, R^(e) can be absent wherethe R³ is a deprotonated carboxylic acid moiety (e.g., where R³ is—CH₂CH₂CO₂ ⁻).

For the imidazolines, R³ can be derived from an acrylic acid. Suitableacrylic acids include, but are not limited to, acrylic acid, methacrylicacid, 2-ethylacrylic acid, 2-propylacrylic acid, and2-(trifluoromethyl)acrylic acid. For example, R³ can be derived fromacrylic acid (H₂C═CHCO₂H).

Imidazolines of formulae (I), (II), or (III) can have R^(x) is—C(R^(a)R^(b))—C(R^(c)R^(d))—CO₂R^(e), wherein R^(a), R^(b), R^(c), andR^(d) are each independently selected from the group consisting ofhydrogen (—H), halogen, and alkyl, and wherein R^(e) is hydrogen (—H) oralkyl. Further, R^(x) can be —C(R^(a)R^(b))—C(R^(c)R^(d))—CO₂R^(e),wherein R^(a), R^(b), R^(c), and R^(d) are each independently selectedfrom the group consisting of hydrogen (—H), halogen, and C₁-C₆-alkyl,and wherein R^(e) is hydrogen (—H) or C₁-C₆-alkyl. Additionally, R^(x)is —CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H) or C₁-C₆-alkyl.Further, R^(e) can be absent where the R^(x) is a deprotonatedcarboxylic acid moiety (e.g., where R^(x) is —CH₂CH₂CO₂ ³¹ ).

For the imidazolines described herein, R^(x) can be derived from anacrylic acid. Suitable acrylic acids include, but are not limited to,acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-propylacrylicacid, and 2-(trifluoromethyl)acrylic acid. For example, R^(x) can bederived from acrylic acid (H₂C═CHCO₂H).

Imidazolines of formulae (I), (II), or (III) can have R⁴ and R⁵ eachindependently be an unsubstituted C₁-C₁₀-alkyl (e.g., methyl, ethyl,propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl,tert-butyl, sec-butyl), pentyl (e.g., n-pentyl, isopentyl, tert-pentyl,neopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl, or decyl)or hydrogen. Further, R⁴ and R⁵ can each independently be anunsubstituted C₁-C₆ alkyl group or hydrogen. Preferably, R⁴ and R⁵ areeach hydrogen (—H).

Imidazolines of formulae (I), (II), or (III) can have R⁶, R⁷, R⁸, R⁹,R¹⁰, and R¹¹ each independently be, at each occurrence, selected fromhydrogen, unsubstituted alkyl, and unsubstituted alkenyl. For example,R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ can each independently be, at eachoccurrence, selected from hydrogen, unsubstituted C₁-C₃₄-alkyl, andunsubstituted C₂-C₃₄-alkenyl. Further, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ caneach independently be, at each occurrence, selected from hydrogen,unsubstituted C₁-C₁₀-alkyl, and unsubstituted C₂-C₁₀-alkenyl.

Further, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ can each independently be, at eachoccurrence, selected from hydrogen, and a radical derived from a fattyacid.

For the imidazoline compounds, R¹² and R¹³ can each independently be, ateach occurrence, selected from hydrogen, C₁-C₁₀-alkyl, —COR¹⁴, —CO₂R¹⁵,—C₁-C₁₀-alkyl-COR¹⁶, and —C₁-C₁₀-alkyl-CO₂R¹⁷. Further, R¹² and R¹³ caneach independently be, at each occurrence, selected from hydrogen,unsubstituted C₁-C₁₀-alkyl, —COR¹⁴, —CO₂R¹⁵, —C₁-C₁₀-alkyl-COR¹⁶, and—C₁-C₁₀-alkyl-CO₂R¹⁷.

For the imidazolines, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ can each independently be,at each occurrence, selected from hydrogen, unsubstituted alkyl, andunsubstituted alkenyl. Further, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ can eachindependently be, at each occurrence, selected from hydrogen,unsubstituted C₁-C₃₄-alkyl, and unsubstituted C₂-C₃₄-alkenyl.Additionally, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ can each independently be, at eachoccurrence, selected from hydrogen, unsubstituted C₁-C₁₀-alkyl, andunsubstituted C₂-C₁₀-alkenyl. Further, R¹⁵ and/or R¹⁷ can be absentwhere the carboxylic acid moiety is deprotonated.

Imidazoline compounds can have R¹⁴, R¹⁵, R¹⁶, and R¹⁷ each independentlybe, at each occurrence, selected from hydrogen, and a radical derivedfrom a fatty acid. Further, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ can eachindependently be, at each occurrence, selected from hydrogen,C₄-C₃₄-alkyl, and C₄-C₃₄-alkenyl. Additionally, R¹⁴, R¹⁵, R¹⁶, and R¹⁷can each independently be, at each occurrence, selected from hydrogen;—(CH₂)₃CH₃; —(CH₂)₄CH₃; —(CH₂)₅CH₃, —(CH₂)₆CH₃; —(CH₂)₇CH₃; —(CH₂)₈CH₃,—(CH₂)₉CH₃; —(CH₂)₁₀CH₃; —(CH₂)₁₁CH₃; —(CH₂)₁₂CH₃; —(CH₂)₁₃CH₃;—(CH₂)₁₄CH₃; —(CH₂)₁₅CH₃; —(CH₂)₁₆CH₃; —(CH₂)₁₇CH₃; —(CH₂)₁₈CH₃;—(CH₂)₁₉CH₃; —(CH₂)₂₀CH₃; —(CH₂)₂₁CH₃; —(CH₂)₂₂CH₃; —(CH₂)₂₃CH₃;—(CH₂)₂₄CH₃; —(CH₂)₂₅CH₃; —(CH₂)₂₆CH₃; —(CH₂)₂₇CH₃; —(CH₂)₂₈CH₃;—(CH₂)₂₉CH₃; —(CH₂)₃₀CH₃; —(CH₂)₃₁CH₃; —(CH₂)₃₂CH₃; —(CH₂)₃₃CH₃;—(CH₂)₃₄CH₃; —(CH₂)₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₃CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₇CH₃;—(CH₂)₃CH═CHCH₂CH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₃CH═CH(CH₂)₄CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₃CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₃CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₃CH═CHCH═CHCH═CHCH═CHCH═CH(CH₂)₄CH₃; —(CH₂)₄CH═CH(CH₂)₈CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH)₄CH₃;—(CH₂)₄CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₅CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₅CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₅CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₆CH═CHCH═CHCH═CH(CH₂)₄CH₃;—(CH₂)₆CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃; —(CH₂)₇CH═CH(CH₂)₃CH₃;—(CH₂)₇CH═CH(CH₂)₅CH₃; —(CH₂)₇CH═CH(CH₂)₇CH₃;—(CH₂)₇CH═CHCH═CHCH═CH(CH₂)₃CH₃; —(CH₂)₇CH═CHCH═CH(CH₂)₅CH₃;—(CH₂)₇CH═CHCH₂CH═CH(CH₂)₄CH₃; —(CH₂)₇CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₇CH═CHCH═CHCH₂CH₂CH═CHCH₂CH₃; —(CH₂)₇CH═CHCH═CHCH═CHCH═CHCH₂CH₃;—(CH₂)₇CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₇CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₇CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃;—(CH₂)₉CH═CH(CH₂)₅CH₃; —(CH₂)₉CH═CHCH₂CH═CH(CH₂)₄CH₃;—(CH₂)₉CH═CHCH₂CH═CHCH₂CH═CHCH₂CH₃; —(CH₂)₉CH═CH(CH₂)₇CH₃;—(CH₂)₁₁CH═CH(CH₂)₅CH₃; —(CH₂)₁₁CH═CH(CH₂)₇CH₃;—(CH₂)₁₁CH═CHCH₂CH═CH(CH₂)₄CH₃; and —(CH₂)₁₃CH═CH(CH₂)₇CH₃.

For the imidazolines of formulae (I), (II), and (III), R¹⁴, R¹⁵, R¹⁶,and R¹⁷ can each independently be, at each occurrence, selected fromhydrogen, a radical derived from a saturated fatty acid, and a radicalderived from an unsaturated fatty acid. Suitable saturated fatty acidsinclude, but are not limited to, butyric acid, valeric acid, caproicacid, enanthic acid, caprylic acid, pelargonic acid, capric acid,undecylic acid, lauric acid, tridecylic acid, myristic acid,pentadecylic acid, palmitic acid, margaric acid, stearic acid,nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid,tricosylic acid, lignoceric acid, pentacosylic acid, cerotic acid,heptacosylic acid, montanic acid, nonacosylic acid, melissic acid,henatriacontylic acid, lacceroic acid, psyllic acid, geddic acid,ceroplastic acid, and hexatriacontylic acid. Suitable unsaturated fattyacids include, but are not limited to, myristoleic acid, palmitoleicacid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleicacid, linoelaidic acid, α-linolenic acid, arachidonic acid,eicosapentaenoic acid, erucic acid, docosahexaenoic acid,hexadecatrienoic acid, stearidonic acid, eicosatrienoic acid,eicosatetraenoic acid, heneicosapentaenoic acid, clupanodonic acid,osbond acid, (9Z,12Z,15Z,18Z,21Z)-tetracosa-9,12,15,18,21-pentaenoicacid, nisinic acid, γ-linolenic acid, eicosadienoic acid,dihomo-γ-linolenic acid, docosadienoic acid, adrenic acid,tetracosatetraenoic acid,(6Z,9Z,12Z,15Z,18Z)-tetracosa-6,9,12,15,18-pentaenoic acid,(Z)-Eicos-11-enoic acid, mead acid, erucic acid, nervonic acid, rumenicacid, α-calendic acid, β-calendic acid, jacaric acid, α-eleostearicacid, β-eleostearic acid, catalpic acid, punicic acid, rumelenic acid,α-parinaric acid, β-parinaric acid, bosseopentaenoic acid, pinolenicacid, and podocarpic acid. Further, R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are eachindependently, at each occurrence, hydrogen or a radical derived fromcoconut oil, beef tallow, or tall oil fatty acids (TOFA).

Preferably, the imidazoline is a compound of formula (I), wherein R¹ isunsubstituted C₂-C₆-alkyl; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e)is absent (e.g., R³ is —CH₂CH₂CO₂ ⁻); R⁴ is hydrogen; and R⁵ ishydrogen.

Alternatively, the imidazoline is a compound of formula (I), wherein R¹is linear C₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² is hydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e)is absent (e.g., R³ is —CH₂CH₂CO₂ ⁻); R⁴ is hydrogen; and R⁵ ishydrogen.

Further, the imidazoline is a compound of formula (I), wherein R¹ islinear C₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² and R¹³ are each a —C₂-alkyl-CO₂R¹⁷, whereinR¹⁷ is hydrogen or is absent (e.g., R¹² is —C₂-alkyl-CO₂ ⁻); R² is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) ishydrogen (—H), C₁-C₆-alkyl, or R^(e) is absent (e.g., R³ is —CH₂CH₂CO₂⁻); R⁴ is hydrogen; and R⁵ is hydrogen.

Additionally, the imidazoline is a compound of formula (II), wherein R¹is unsubstituted C₂-C₆-alkyl; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e)is absent (e.g., R³ is —CH₂CH₂CO₂ ⁻); R^(x) is —CH₂CH₂CO₂R^(e), whereinR^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e) is absent (e.g., R^(x) is—CH₂CH₂CO₂ ⁻); R⁴ is hydrogen; and R⁵ is hydrogen.

The imidazoline can be a compound of formula (II), wherein R¹ is linearC₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² is hydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e)is absent (e.g., R³ is —CH₂CH₂CO₂ ⁻); R^(x) is —CH₂CH₂CO₂R^(e), whereinR^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e) is absent (e.g., R^(x) is—CH₂CH₂CO₂); R⁴ is hydrogen; and R⁵ is hydrogen.

The imidazoline can be a compound of formula (II), wherein R¹ is linearC₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² and R¹³ are each a —C₂-alkyl-CO₂R¹⁷, whereinR¹⁷ is hydrogen or is absent (e.g., R¹² is —C₂-alkyl-CO₂ ⁻); R² is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) ishydrogen (—H), C₁-C₆-alkyl, or R^(e) is absent (e.g., R³ is —CH₂CH₂CO₂⁻); R^(x) is —CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H),C₁-C₆-alkyl, or R^(e) is absent (e.g., R^(x) is —CH₂CH₂CO₂); R⁴ ishydrogen; and R⁵ is hydrogen.

The imidazoline can be a compound of formula (III), wherein R¹ isunsubstituted C₂-C₆-alkyl; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ ishydrogen; and R⁵ is hydrogen.

The imidazoline can be a compound of formula (III), wherein R¹ is linearC₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² is hydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ ishydrogen; and R⁵ is hydrogen.

The imidazoline can be a compound of formula (III), wherein R¹ is linearC₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² and R¹³ are each a —C₂-alkyl-CO₂R¹⁷, whereinR¹⁷ is hydrogen or is absent (e.g., R¹² is —C₂-alkyl-CO₂ ⁻); R² is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ is hydrogen; and R⁵ is hydrogen.

It is to be understood, whether explicitly set forth or not, thatformula (I), formula (II), and formula (III) are each intended toencompass the tautomeric, racemic, enantiomeric, diastereomeric,zwitterionic, and salt forms of said formulas. The imidazolines canexist in a zwitterionic form where R³ and/or R^(x) is derived from anacrylic acid.

The imidazoline compound can be present in the compositions in an amountof 1 wt % to 50 wt %, 2 wt % to 40 wt %, 3 wt % to 30 wt %, 4 wt % to 20wt %, 5 wt % to 17 wt %, 6 wt % to 16 wt %, 7 wt % to 15 wt %, 8 wt % to14 wt %, 9 wt % to 13 wt %, or 10 wt % to 12 wt %, based on total weightof the composition. The imidazoline compound can constitute about 1 wt%, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %,about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %,about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt%, about 17 wt %, about 18 wt %, about 19 wt %, or about 20 wt % of thecomposition, based on total weight of the composition. The compositioncan comprise about 11 wt % of the imidazoline compound, based on totalweight of the composition. The composition can comprise 11 wt % of theimidazoline compound, based on total weight of the composition.

b. Quaternary Amines

The compositions disclosed herein include a quaternary amine. Suitablequaternary amines include, but are not limited to, alkyl, hydroxyalkyl,alkylaryl, arylalkyl or arylamine quaternary salts.

Suitable alkyl, hydroxyalkyl, alkylaryl arylalkyl or arylaminequaternary salts include those alkylaryl, arylalkyl and arylaminequaternary salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻] whereinR^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbon atoms, and Xis Cl, Br or I. For the quaternary amine, R^(5a), R^(6a), R^(7a), andR^(8a) can each independently be selected from the group consisting ofalkyl (e.g., C₁-C₁₈ alkyl), hydroxyalkyl (e.g., C₁-C₁₈ hydroxyalkyl),and arylalkyl (e.g., benzyl). The mono or polycyclic aromatic amine saltwith an alkyl or alkylaryl halide include salts of the formula[N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻] wherein R^(5a), R^(6a), R^(7a), andR^(8a) contain one to 18 carbon atoms, and X is Cl, Br or I.

Suitable quaternary ammonium salts include, but are not limited to,tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropylammonium chloride, tetrabutyl ammonium chloride, tetrahexyl ammoniumchloride, tetraoctyl ammonium chloride, benzyltrimethyl ammoniumchloride, benzyltriethyl ammonium chloride, phenyltrimethyl ammoniumchloride, phenyltriethyl ammonium chloride, cetyl benzyldimethylammonium chloride, hexadecyl trimethyl ammonium chloride, dimethyl alkylbenzyl quaternary ammonium compounds, monomethyl dialkyl benzylquaternary ammonium compounds, trimethyl benzyl quaternary ammoniumcompounds, and trialkyl benzyl quaternary ammonium compounds, whereinthe alkyl group can contain between about 1 and about 24 carbon atoms,about 10 and about 18 carbon atoms, or about 12 to about 16 carbonatoms, such as for example, C₁₂-₁₆ benzyl dimethyl ammonium chloride.Suitable quaternary ammonium compounds (quats) include, but are notlimited to, trialkyl, dialkyl, dialkoxy alkyl, monoalkoxy, benzyl, andimidazolinium quaternary ammonium compounds, salts thereof, the like,and combinations thereof. The quaternary ammonium salt can be analkylamine benzyl quaternary ammonium salt, a benzyl triethanolaminequaternary ammonium salt, or a benzyl dimethylaminoethanolaminequaternary ammonium salt.

The quaternary amine can be a benzalkonium salt represented by theformula:

wherein n is 8, 10, 12, 14, 16, or 18; and X is Cl, Br or I.

The quaternary amine can be a mixture of benzalkonium salts wherein n is8, 10, 12, 14, 16, and 18.

The quaternary amine can be a mixture of benzalkonium salts wherein n is12, 14, 16, and 18.

The quaternary amine can be a mixture of benzalkonium salts wherein n is12, 14, and 16.

The quaternary amine can be a mixture of benzalkonium salts wherein n is12, 14, 16, and 18 and X is Cl.

The quaternary amine can be a mixture of benzalkonium salts wherein n is12, 14, and 16, and X is Cl.

The quaternary amine can be an alkyl pyridinium quaternary salt such asthose represented by the general formula:

wherein R^(9a) is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atoms and B isCl, Br or I. Among these compounds are alkyl pyridinium salts and alkylpyridinium benzyl quats. Exemplary compounds include methyl pyridiniumchloride, ethyl pyridinium chloride, propyl pyridinium chloride, butylpyridinium chloride, octyl pyridinium chloride, decyl pyridiniumchloride, lauryl pyridinium chloride, cetyl pyridinium chloride, benzylpyridinium and an alkyl benzyl pyridinium chloride, preferably whereinthe alkyl is a C₁-C₆ hydrocarbyl group.

The quaternary amine can be present in the compositions in an amount of0.1 wt % to 80 wt %, 1 wt % to 40 wt %, 5 wt % to 35 wt %, 10 wt % to 30wt %, 15 wt % to 25 wt %, 16 wt % to 24 wt %, 17 wt % to 23 wt %, 18 wt% to 22 wt %, or 19 wt % to 21 wt %, based on total weight of thecomposition. The quaternary amine constitutes about 5 wt %, about 6 wt%, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt%, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about 16wt %, about 17 wt %, about 18 wt %, about 19 wt %, about 20 wt %, about21 wt %, about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt %,about 26 wt %, about 27 wt %, about 28 wt %, about 29 wt %, about 30 wt%, about 31 wt %, about 32 wt %, about 33 wt %, about 34 wt %, or about35 wt % of the composition, based on total weight of the composition.The quaternary amine is present in an amount of about 20 wt % or about21 wt %, based on total weight of the composition. The quaternary amineis present in an amount of 20.5 wt %, based on total weight of thecomposition.

The composition can include 5 wt % to 35 wt % of quaternary aminecomprising C₁₂-benzyl dimethyl ammonium chloride (e.g., 4 wt % to 20 wt%, based on total weight of the composition), C₁₄-benzyl dimethylammonium chloride (e.g., 1 wt % to 10 wt %, based on total weight of thecomposition), C₁₆-benzyl dimethyl ammonium chloride (e.g., 0.1 wt % to 5wt %, based on total weight of the composition), and C₁₈-benzyl dimethylammonium chloride (e.g., 0.5 wt % or less, based on total weight of thecomposition). The composition can include about 20 wt % or about 21 wt %of quaternary amine comprising C₁₂-benzyl dimethyl ammonium chloride(e.g., 14.5 wt %, based on total weight of the composition), C₁₄-benzyldimethyl ammonium chloride (e.g., 5 wt %, based on total weight of thecomposition), C₁₆-benzyl dimethyl ammonium chloride (e.g., 1 wt %, basedon total weight of the composition), and C₁₈-benzyl dimethyl ammoniumchloride (e.g., 0.2 wt % or less, based on total weight of thecomposition).

c. Phosphonium Compounds

The compositions disclosed herein include at least one phosphoniumcompound, and in particular, a phosphonium salt. Suitable phosphoniumsalts include, but are not limited to,alkyltris(hydroxyorgano)phosphonium salts,alkenyltris(hydroxyorgano)phosphonium salts, andtetrakis(hydroxyorgano)phosphonium salts. Thealkyltris(hydroxyorgano)phosphonium salts can beC₁-C₃-alkyltris(hydroxymethyl)phosphonium salts. Thealkenyltris(hydroxyorgano)phosphonium salts can beC₂-C₃-alkenyltris(hydroxymethyl)phosphonium salts. Thetetrakis(hydroxyorgano)phosphonium salts can betetrakis(hydroxymethyl)phosphonium salts, including, but not limited to,tetrakis(hydroxymethyl)phosphonium sulphate (THPS),tetrakis(hydroxymethyl)phosphonium chloride,tetrakis(hydroxymethyl)phosphonium phosphate,tetrakis(hydroxymethyl)phosphonium formate,tetrakis(hydroxymethyl)phosphonium acetate, andtetrakis(hydroxymethyl)phosphonium oxalate. The phosphonium salt can betetrakis(hydroxymethyl)phosphonium sulphate (THPS).

The phosphonium salt can be present in the compositions in an amount of0.1 wt % to 80 wt %, 0.5 wt % to 50 wt %, 1 wt % to 14 wt %, 2 wt % to13 wt %, 3 wt % to 12 wt %, 4 wt % to 11 wt %, 5 wt % to 10 wt %, 6 wt %to 9 wt %, or 7 wt % to 8 wt %, based on total weight of thecomposition. The phosphonium salt constitutes about 1 wt %, about 2 wt%, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %,about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %,about 13 wt %, or about 14 wt % of the composition, based on totalweight of the composition The phosphonium salt can be present in anamount of about 7 wt %, based on total weight of the composition. Thephosphonium salt can be present in an amount of 7.5 wt %, based on totalweight of the composition.

d. Demulsifiers

The compositions disclosed herein can include a demulsifier (alsoreferred to as an emulsion breaker). Suitable emulsion breakers include,but are not limited to, dodecylbenzylsulfonic acid (DDBSA), the sodiumsalt of xylenesulfonic acid (NAXSA), epoxylated and propoxylatedcompounds, anionic cationic and nonionic surfactants, and resins, suchas polyoxyalkylenes, vinyl polymers, polyamines, polyamides, phenolics,and silicone polyethers. The emulsion breaker can be a vinyl polymer,such as: acrylic acid, polymer with t-butylphenol, formaldehyde, maleicanhydride, propylene oxide, and ethylene oxide (CAS Registry Number:178603-70-8).

The demulsifier can be present in an amount of 0.1 wt % to 30 wt %, 0.5wt % to 10 wt %, or 1 wt % to 5 wt %, based on total weight of thecomposition. The demulsifier constitutes about 1 wt %, about 2 wt %,about 3 wt %, about 4 wt %, or about 5 wt % of the composition, based ontotal weight of the composition. The compositions comprise about 2 wt %or about 3 wt % of the demulsifier, based on total weight of thecomposition. The composition comprises 2.6 wt % of the demulsifier,based on total weight of the composition.

e. Synergist

The compositions disclosed herein can include a synergistic component.Suitable synergist compounds include, but are not limited to,thioglycolic acid, 3,3′-dithiodipropionic acid, thiosulfate, thiourea,2-mercaptoethanol, L-cysteine, and tert-butyl mercaptan. The synergisticcompound can be 2-mercaptoethanol.

The synergist can be present in an amount of 0.01 wt % to 10 wt %, 0.1wt % to 8 wt %, 0.5 wt % to 7 wt %, 1 wt % to 6 wt %, 2 wt % to 5 wt %,or 3 wt % to 4 wt %, based on total weight of the composition. Thesynergist can constitute about 0.5 wt %, about 1 wt %, about 1.5 wt %,about 2.0 wt %, about 2.5 wt %, about 3.0 wt %, about 3.5 wt %, about4.0 wt %, about 4.5 wt %, about 5.0 wt %, about 5.5 wt %, or about 6.0wt % of the composition, based on total weight of the composition. Thecomposition can comprise about 3.5 wt % of the synergist, based on totalweight of the composition. The composition can comprise 3.5 wt % of thesynergist, based on total weight of the composition.

f. Solvents

The compositions disclosed herein can include a solvent. Suitablesolvents include, but are not limited to, alcohols, hydrocarbons,ketones, ethers, aromatics, amides, nitriles, sulfoxides, esters, glycolethers, aqueous systems, and combinations thereof. The solvent can bewater, isopropanol, methanol, ethanol, 2-ethylhexanol, heavy aromaticnaphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether(EGMBE), diethylene glycol monoethyl ether, or xylene. Representativepolar solvents suitable for formulation with the composition includewater, brine, seawater, alcohols (including straight chain or branchedaliphatic such as methanol, ethanol, propanol, isopropanol, butanol,2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.),glycols and derivatives (ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, ethylene glycol monobutyl ether, etc.), ketones(cyclohexanone, diisobutylketone), N-methylpyrrolidinone (NMP),N,N-dimethylformamide and the like. Representative non-polar solventssuitable for formulation with the composition include aliphatics such aspentane, hexane, cyclohexane, methylcyclohexane, heptane, decane,dodecane, diesel, and the like; aromatics such as toluene, xylene, heavyaromatic naphtha, fatty acid derivatives (acids, esters, amides), andthe like.

The solvent can be methanol, isopropanol, 2-ethylhexanol, or acombination thereof. Further, the solvent can be methanol, isopropanol,2-ethylhexanol, water, or a combination thereof.

A composition of the invention can comprise from 0 to 99 percent, 1 to98 percent, 10 to 80 percent, 20 to 70 percent, 30 to 60 percent, or 40to 55 percent by weight of one or more solvents, based on total weightof the composition.

A composition of the invention can comprise about 20%, about 25%, about30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%,about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, orabout 95% by weight of one or more solvents, based on total weight ofthe composition. A composition of the invention comprises about 40% ofone or more alcoholic solvents and about 15% of water. A composition ofthe invention can comprise about 40% of a methanol/isopropanol mixtureand about 15% of water. A composition of the invention can comprise 40%of a methanol/isopropanol mixture and 14.9% of water.

The compositions of the invention optionally include one or moreadditional additives. Suitable additives include, but are not limitedto, corrosion inhibitors, asphaltene inhibitors, paraffin inhibitors,scale inhibitors, emulsifiers, water clarifiers, dispersants, hydrogensulfide scavengers, gas hydrate inhibitors, biocides, pH modifiers, andsurfactants.

g. Corrosion Inhibitors

Suitable corrosion inhibitors for inclusion in the compositions include,but are not limited to, mono-, di- or trialkyl or alkylaryl phosphateesters; phosphate esters of hydroxylamines; phosphate esters of polyols;and monomeric or oligomeric fatty acids.

Suitable mono-, di- and trialkyl as well as alkylaryl phosphate estersand phosphate esters of mono, di, and triethanolamine typically containbetween from 1 to about 18 carbon atoms. Preferred mono-, di- andtrialkyl phosphate esters, alkylaryl or arylalkyl phosphate esters arethose prepared by reacting a C₃-C₁₈ aliphatic alcohol with phosphorouspentoxide. The phosphate intermediate interchanges its ester groups withtriethyl phosphate with triethylphosphate producing a more broaddistribution of alkyl phosphate esters. Alternatively, the phosphateester can be made by admixing with an alkyl diester, a mixture of lowmolecular weight alkyl alcohols or diols. The low molecular weight alkylalcohols or diols preferably include C₆ to C₁₀ alcohols or diols.Further, phosphate esters of polyols and their salts containing one ormore 2-hydroxyethyl groups, and hydroxylamine phosphate esters obtainedby reacting polyphosphoric acid or phosphorus pentoxide withhydroxylamines such as diethanolamine or triethanolamine are preferred.

The corrosion inhibitor can be a monomeric or oligomeric fatty acid.Preferred are C₁₄-C₂₂ saturated and unsaturated fatty acids as well asdimer, trimer and oligomer products obtained by polymerizing one or moreof such fatty acids.

h. Asphaltene Inhibitors

Suitable asphaltene inhibitors include, but are not limited to,aliphatic sulphonic acids; alkyl aryl sulphonic acids; aryl sulfonates;lignosulfonates; alkylphenol/aldehyde resins and similar sulfonatedresins; polyolefin esters; polyolefin imides; polyolefin esters withalkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefinamides; polyolefin amides with alkyl, alkylenephenyl or alkylenepyridylfunctional groups; polyolefin imides with alkyl, alkylenephenyl oralkylenepyridyl functional groups; alkenyl/vinyl pyrrolidone copolymers;graft polymers of polyolefins with maleic anhydride or vinyl imidazole;hyperbranched polyester amides; polyalkoxylated asphaltenes, amphotericfatty acids, salts of alkyl succinates, sorbitan monooleate, andpolyisobutylene succinic anhydride.

i. Paraffin Inhibitors

Suitable paraffin inhibitors include, but are not limited to, paraffincrystal modifiers, and dispersant/crystal modifier combinations.Suitable paraffin crystal modifiers include, but are not limited to,alkyl acrylate copolymers, alkyl acrylate vinylpyridine copolymers,ethylene vinyl acetate copolymers, maleic anhydride ester copolymers,branched polyethylenes, naphthalene, anthracene, microcrystalline waxand/or asphaltenes. Suitable dispersants include, but are not limitedto, dodecyl benzene sulfonate, oxyalkylated alkylphenols, andoxyalkylated alkylpnenolic resins.

j. Scale Inhibitors

Suitable scale inhibitors include, but are not limited to, phosphates,phosphate esters, phosphoric acids, phosphonates, phosphonic acids,polyacrylamides, salts of acrylamido-methyl propane sulfonate/acrylicacid copolymer (AMPS/AA), phosphinated maleic copolymer (PHOS/MA), andsalts of a polymaleic acid/acrylic acid/acrylamido-methyl propanesulfonate terpolymer (PMA/AMPS).

k. Emulsifiers

Suitable emulsifiers include, but are not limited to, salts ofcarboxylic acids, products of acylation reactions between carboxylicacids or carboxylic anhydrides and amines, and alkyl, acyl and amidederivatives of saccharides (alkyl-saccharide emulsifiers).

l. Water Clarifiers

Suitable water clarifiers include, but are not limited to, inorganicmetal salts such as alum, aluminum chloride, and aluminum chlorohydrate,or organic polymers such as acrylic acid based polymers, acrylamidebased polymers, polymerized amines, alkanolamines, thiocarbamates, andcationic polymers such as diallyldimethylammonium chloride(DADMAC).

m. Dispersants

Suitable dispersants include, but are not limited to, aliphaticphosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonicacid, and aminoalkyl phosphonic acids, e.g. polyaminomethylenephosphonates with 2-10 N atoms e.g. each bearing at least one methylenephosphonic acid group; examples of the latter are ethylenediaminetetra(methylene phosphonate), diethylenetriamine penta(methylenephosphonate) and the triamine- and tetramine-polymethylene phosphonateswith 2-4 methylene groups between each N atom, at least 2 of the numbersof methylene groups in each phosphonate being different. Other suitabledispersion agents include lignin or derivatives of lignin such aslignosulfonate and naphthalene sulfonic acid and derivatives.

n. Hydrogen Sulfide Scavengers

Suitable additional hydrogen sulfide scavengers include, but are notlimited to, oxidants (e.g., inorganic peroxides such as sodium peroxide,or chlorine dioxide), aldehydes (e.g., of 1-10 carbons such asformaldehyde or glutaraldehyde or (meth)acrolein), triazines (e.g.,monoethanol amine triazine, monomethylamine triazine, and triazines frommultiple amines or mixtures thereof), and glyoxal.

o. Gas Hydrate Inhibitors

Suitable gas hydrate inhibitors include, but are not limited to,thermodynamic hydrate inhibitors (THI), kinetic hydrate inhibitors(KHI), and anti-agglomerates (AA). Suitable thermodynamic hydrateinhibitors include, but are not limited to, NaCl salt, KCl salt, CaCl₂salt, MgCl₂ salt, NaBr₂ salt, formate brines (e.g. potassium formate),polyols (such as glucose, sucrose, fructose, maltose, lactose,gluconate, monoethylene glycol, diethylene glycol, triethylene glycol,mono-propylene glycol, dipropylene glycol, tripropylene glycols,tetrapropylene glycol, monobutylene glycol, dibutylene glycol,tributylene glycol, glycerol, diglycerol, triglycerol, and sugaralcohols (e.g. sorbitol, mannitol)), methanol, propanol, ethanol, glycolethers (such as diethyleneglycol monomethylether, ethyleneglycolmonobutylether), and alkyl or cyclic esters of alcohols (such as ethyllactate, butyl lactate, methylethyl benzoate). Suitable kinetic hydrateinhibitors and anti-agglomerates include, but are not limited to,polymers and copolymers, polysaccharides (such as hydroxy-ethylcellulose(HEC), carboxymethylcellulose (CMC), starch, starch derivatives, andxanthan), lactams (such as polyvinylcaprolactam, polyvinyl lactam),pyrrolidones (such as polyvinyl pyrrolidone of various molecularweights), surfactants (such as fatty acid salts, ethoxylated alcohols,propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters,polyglycerol esters of fatty acids, alkyl glucosides, alkylpolyglucosides, alkyl sulfates, alkyl sulfonates, alkyl estersulfonates, alkyl aromatic sulfonates, alkyl betaine, alkyl amidobetaines), hydrocarbon based dispersants (such as lignosulfonates,iminodisuccinates, polyaspartates), amino acids, and proteins.

p. Biocides

Suitable additional biocides include, but are not limited to, oxidizingand non-oxidizing biocides. Suitable non-oxidizing biocides include, forexample, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein),amine-type compounds (e.g., quaternary amine compounds and cocodiamine),halogenated compounds (e.g., bronopol and2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (e.g.,isothiazolone, carbamates, and metronidazole), and quaternaryphosphonium salts (e.g., tetrakis(hydroxymethyl)phosphonium sulfate(THPS)). Suitable oxidizing biocides include, for example, sodiumhypochlorite, trichloroisocyanuric acids, dichloroisocyanuric acid,calcium hypochlorite, lithium hypochlorite, chlorinated hydantoins,stabilized sodium hypobromite, activated sodium bromide, brominatedhydantoins, chlorine dioxide, ozone, and peroxides.

q. pH Modifiers

Suitable pH modifiers include, but are not limited to, alkalihydroxides, alkali carbonates, alkali bicarbonates, alkaline earth metalhydroxides, alkaline earth metal carbonates, alkaline earth metalbicarbonates and mixtures or combinations thereof. Exemplary pHmodifiers include NaOH, KOH, Ca(OH)₂, CaO, Na₂CO₃, KHCO₃, K₂CO₃, NaHCO₃,MgO, and Mg(OH)₂.

r. Surfactants

Suitable surfactants include, but are not limited to, anionicsurfactants, cationic surfactants, zwitterionic surfactants, andnonionic surfactants. Anionic surfactants include alkyl aryl sulfonates,olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ethersulfates, alkyl carboxylates and alkyl ether carboxylates, and alkyl andethoxylated alkyl phosphate esters, and mono and dialkyl sulfosuccinatesand sulfosuccinamates. Cationic surfactants include alkyl trimethylquaternary ammonium salts, alkyl dimethyl benzyl quaternary ammoniumsalts, dialkyl dimethyl quaternary ammonium salts, and imidazoliniumsalts. Nonionic surfactants include alcohol alkoxylates, alkylphenolalkoxylates, block copolymers of ethylene, propylene and butyleneoxides, alkyl dimethyl amine oxides, alkyl-bis(2-hydroxyethyl) amineoxides, alkyl amidopropyl dimethyl amine oxides,alkylamidopropyl-bis(2-hydroxyethyl) amine oxides, alkyl polyglucosides,polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitanesters, and alkoyl polyethylene glycol esters and diesters. Alsoincluded are betaines and sultanes, amphoteric surfactants such as alkylamphoacetates and amphodiacetates, alkyl amphopropripionates andamphodipropionates, and alkyliminodiproprionate.

The surfactant can be a quaternary ammonium compound, an amine oxide, anionic or non-ionic surfactant, or any combination thereof. Suitablequaternary amine compounds include, but are not limited to, alkyl benzylammonium chloride, benzyl cocoalkyl(C₁₂-C₁₈)dimethylammonium chloride,dicocoalkyl (C₁₂-C₁₈)dimethylammonium chloride, ditallowdimethylammonium chloride, di(hydrogenated tallow alkyl)dimethylquaternary ammonium methyl chloride, methyl bis(2-hydroxyethylcocoalkyl(C₁₂-C₁₈) quaternary ammonium chloride, dimethyl(2-ethyl)tallow ammonium methyl sulfate, n-dodecylbenzyldimethylammoniumchloride, n-octadecylbenzyldimethyl ammonium chloride,n-dodecyltrimethylammonium sulfate, soya alkyltrimethylammoniumchloride, and hydrogenated tallow alkyl (2-ethylhyexyl) dimethylquaternary ammonium methyl sulfate.

s. Additional Components

Compositions made according to the invention can further includeadditional functional agents or additives that provide a beneficialproperty. Additional agents or additives will vary according to theparticular composition being manufactured and its intended use as oneskilled in the art will appreciate.

Alternatively, the compositions do not contain any of the additionalagents or additives.

3. SYNTHESIS

The compounds and compositions of the invention can be better understoodin connection with the following synthetic schemes and methods whichillustrate a means by which the compounds can be prepared.

As shown in Scheme 1, compounds of formula (1) can be prepared byreacting an imidazoline of formula (2) with an acrylic acid of formula(3), wherein R¹, R², R³, R⁴, R⁵, R^(a), R^(b), R^(c), and R^(e) are asdefined above. The imidazoline of formula (2) can be prepared fromreacting a diamine, such as ethylene diamine (EDA), diethylene triamine(DETA), or triethylene tetraamine (TETA) with a long chain fatty acid,such as tall oil fatty acid (TOFA). The compound of formula (3)introduced in the representative reaction schemes generally includeα,β-unsaturated carboxylic fatty acids and amide and ester derivativesthereof; unsaturated sulfonic and phosphonic fatty acids; and theircombinations. The compound of formula (3) can be selected from the groupconsisting of substituted and unsubstituted α,β-unsaturated carboxylicfatty acids and amide and ester derivatives thereof, having from 3 toabout 11 carbon atoms, or a salt thereof; substituted and unsubstitutedα,β-unsaturated fatty acids having from 2 to about 11 carbon atoms, or asalt thereof, and combinations thereof.

For Scheme 1, R⁴, R⁵, R^(a), R^(b), R^(e), and R^(e) are each hydrogen.Additionally, R¹ is C₂-C₁₀-alkyl, C₂-C₅-alkyl, or C₂-C₆-alkyl; and R⁴,R⁵, R^(a), R^(b), R^(c), and R^(e) are each hydrogen. Further, R¹ isC₂-C₁₀-alkyl, C₂-C₈-alkyl, or C₂-C₆-alkyl; R² is a C₁₇ radical; and R⁴,R⁵, R^(a), R^(b), R^(e), and R^(e) are each hydrogen. Also, R¹ isC₂-C₁₀-alkyl, C₂-C₈-alkyl, or C₂-C₆-alkyl; R² is a radical derived fromcoconut oil, beef tallow, or tall oil fatty acids (TOFA); and R⁴, R⁵,R^(a), R^(b), R^(e), and R^(e) are each hydrogen.

As shown in Scheme 2, compounds of formula (4) can be prepared byreacting an imidazoline of formula (2) with an acrylic acid of formula(3), wherein R¹, R², R³, R^(x), R⁴, R⁵, R^(a), R^(b), R^(c), and R^(e)are as defined above.

For Scheme 2, R⁴, R⁵, R^(a), R^(b), R^(c), and R^(e) are each hydrogen.Additionally, R¹ is linear C₂-alkyl, substituted with one substituentthat is a terminal —N(R¹²)(R¹³), wherein R¹² is hydrogen and R¹³ is—COR¹⁴, wherein R¹⁴ is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R² is —C₁₇H₃₅,—C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen(—H), C₁-C₆-alkyl, or R^(e) is absent (e.g., R³ is —CH₂CH₂CO₂ ⁻); R^(x)is —CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H), C₁-C₆-alkyl, orR^(e) is absent (e.g., R^(x) is —CH₂CH₂CO₂ ⁻); R⁴ is hydrogen; and R⁵ ishydrogen. Further, R¹ is linear C₂-alkyl, substituted with onesubstituent that is a terminal —N(R¹²)(R¹³), wherein R¹² and R¹³ areeach a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷ is hydrogen or is absent (e.g., R¹²is —C₂-alkyl -CO₂ ⁻); R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e)is absent (e.g., R³ is —CH₂CH₂CO₂ ⁻); R^(x) is —CH₂CH₂CO₂R^(e), whereinR^(e) is hydrogen (—H), C₁-C₆-alkyl, or R^(e) is absent (e.g., R^(x) is—CH₂CH₂CO₂ ⁻); R⁴ is hydrogen; and R⁵ is hydrogen.

Imidazolines for use with compositions of the invention can also becommercially available.

The compounds can be further modified, for example, by manipulation ofsubstituents. These manipulations can include, but are not limited to,reduction, oxidation, organometallic cross-coupling, alkylation,acylation, and hydrolysis reactions which are commonly known to thoseskilled in the art. In some cases, the order of carrying out theforegoing reaction schemes can be varied to facilitate the reaction orto avoid unwanted reaction products.

4. Methods of Use

The compositions of the invention can be used in any industry where itis desirable to control biofouling and/or inhibit corrosion at asurface. The compositions can preferably be used as biocides for use inoil and gas applications. By treating a gas or liquid stream with aneffective amount of a composition of the invention, the compositions canprovide significant planktonic kill and enhanced biofilm control bydelaying regrowth kinetics of the biofilms.

The compositions can be used in water systems, condensate/oilsystems/gas systems, or any combination thereof.

The compositions can be applied to a gas or liquid produced or used inthe production, transportation, storage, and/or separation of crude oilor natural gas.

The compositions can be applied to a gas stream used or produced in acoal-fired process, such as a coal-fired power plant.

The compositions can be applied to a gas or liquid produced or used in awaste-water process, a farm, a slaughter house, a land-fill, amunicipality waste-water plant, a coking coal process, or a biofuelprocess.

A fluid to which the compositions can be introduced can be an aqueousmedium. The aqueous medium can comprise water, gas, and optionallyliquid hydrocarbon. A fluid to which the compositions can be introducedcan be a liquid hydrocarbon. The liquid hydrocarbon can be any type ofliquid hydrocarbon including, but not limited to, crude oil, heavy oil,processed residual oil, bitminous oil, coker oils, coker gas oils, fluidcatalytic cracker feeds, gas oil, naphtha, fluid catalytic crackingslurry, diesel fuel, fuel oil, jet fuel, gasoline, and kerosene. Thefluid or gas can be a refined hydrocarbon product.

A fluid or gas treated with a composition of the invention can be at anyselected temperature, such as ambient temperature or an elevatedtemperature. The fluid (e.g., liquid hydrocarbon) or gas can be at atemperature of from about 40° C. to about 250° C. The fluid or gas canbe at a temperature of from −50° C. to 300° C., 0° C. to 200° C., 10° C.to 100° C., or 20° C. to 90° C.

The compositions of the invention can be added to a fluid at variouslevels of water cut. For example, the water cut can be from 0% to 100%volume/volume (v/v), from 1% to 80% v/v, or from 1% to 60% v/v. Thefluid can be an aqueous medium that contains various levels of salinity.The fluid can have a salinity of 0% to 25%, about 1% to 24%, or about10% to 25% weight/weight (w/w) total dissolved solids (TDS).

The fluid or gas in which the compositions of the invention areintroduced can be contained in and/or exposed to many different types ofapparatuses. For example, the fluid or gas can be contained in anapparatus that transports fluid or gas from one point to another, suchas an oil and/or gas pipeline. The apparatus can be part of an oiland/or gas refinery, such as a pipeline, a separation vessel, adehydration unit, or a gas line. The fluid can be contained in and/orexposed to an apparatus used in oil extraction and/or production, suchas a wellhead. The apparatus can be part of a coal-fired power plant.The apparatus can be a scrubber (e.g., a wet flue gas desulfurizer, aspray dry absorber, a dry sorbent injector, a spray tower, a contact orbubble tower, or the like). The apparatus can be a cargo vessel, astorage vessel, a holding tank, or a pipeline connecting the tanks,vessels, or processing units. The fluid or gas can be contained in watersystems, condensate/oil systems/gas systems, or any combination thereof.

The compositions of the invention can be introduced into a fluid or gasby any appropriate method for ensuring dispersal through the fluid orgas. The inhibitor composition is added at a point in a flow lineupstream from the point at which corrosion prevention is desired. Thecompositions can be injected using mechanical equipment such as chemicalinjection pumps, piping tees, injection fittings, atomizers, quills, andthe like. The compositions of the invention can be introduced with orwithout one or more additional polar or non-polar solvents dependingupon the application and requirements. The compositions of the inventioncan be pumped into an oil and/or gas pipeline using an umbilical line.Capillary injection systems can be used to deliver the compositions to aselected fluid. The compositions can be introduced into a liquid andmixed. The compositions can be injected into a gas stream as an aqueousor nonaqueous solution, mixture, or slurry. The fluid or gas can bepassed through an absorption tower comprising a compound or compositionof the invention.

The compositions can be applied to a fluid or gas to provide anyselected concentration. In practice, the compositions of the inventionare typically added to a flow line to provide an effective treating doseof the described compositions from about 0.01 to about 10,000 ppm. Thecompositions can be applied to a fluid or gas to provide a total actives(e.g., imidazoline, quaternary amine, phosphonium salt, demulsifier, andsynergist) concentration of about 1 parts per million (ppm) to about1,000,000 ppm, about 1 ppm to about 100,000 ppm, about 10 ppm to about75,000 ppm, about 10 ppm to about 10,000 ppm, about 50 ppm to about10,000 ppm, or about 100 ppm to about 500 ppm. The compositions can beapplied to a fluid to provide an actives concentration of about 10 ppmto about 10,000 ppm, about 10 ppm to about 500 ppm, about 50 ppm toabout 500 ppm, or about 100 ppm to about 500 ppm. The compositions areapplied to a fluid or gas to provide an actives concentration of about50 ppm, about 100 ppm, about 150 ppm, about 200 ppm, about 250 ppm,about 300 ppm, about 350 ppm, about 400 ppm, about 450 ppm, about 500ppm, about 550 ppm, about 600 ppm, about 650 ppm, about 700 ppm, about750 ppm, about 800 ppm, about 850 ppm, about 900 ppm, about 950 ppm, orabout 1,000 ppm. Each system can have its own dose level requirements,and the effective dose level of a composition to sufficiently reduce therate of corrosion can vary with the system in which it is used.

The compositions can be applied continuously, in batch, or a combinationthereof. The composition doses can be continuous.

The composition doses can be intermittent (i.e., batch treatment).

The composition doses can be continuous/maintained and/or intermittent.

Dosage rates for continuous treatments typically range from about 10 toabout 500 ppm, or about 10 to about 200 ppm.

Dosage rates for batch treatments typically range from about 10 to about10,000 ppm.

The composition can be applied as a pill to a pipeline, providing a highdose (e.g., 10,000 ppm) of the composition.

The flow rate of a flow line in which the composition is used can bebetween 0 and 100 feet per second, or between 0.1 and 50 feet persecond. In some cases, the compositions can be formulated with water inorder to facilitate addition to the flow line.

The compositions can provide 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%,90%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%,99.7%, 99.8%, 99.9%, or 100% planktonic kill. The compositions canprovide 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%,99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or100% planktonic kill in a dynamic flow loop test after a 4-hour contactperiod with the biocide composition.

The dynamic flow loop can be characterized by a test system that holdsapproximately a selected volume of fluid (e.g., 1.5 liters) that arecontinually circulated over 1018 carbon steel biostuds (e.g., located inthe 6 o'clock position of a modified Robbin's device). The test fluidcan be pumped through the system at a selected rate (e.g., approximately3.1 gallons per minute), which allows for deposition of microorganismsand solids onto the biostuds. The health of the microbial population canbe monitored (e.g., weekly) during the biofilm growth period (e.g., 7weeks) using ATP quantification. After concluding the establishment of amature biofilm, a biocide efficacy study can be initiated. During thestudy, solid and fluid samples can be collected before and after thebiocide treatment at scheduled intervals (e.g., 4 hours, 24 hours, 72hours, or 120 hours). A baseline reading (e.g., solid and fluid samples)can be taken prior to the addition of the biocide to the individual flowloop. To study how quickly a biofilm is able to regrow after batchbiocide treatment, the total biocide-treated fluid in each flow loop canbe removed from the system and untreated production fluid added backinto the system. Additional solid samples (e.g., biostuds) can beremoved at selected time intervals (e.g., 24, 48 and either 72 or120-hours) after the new fluid was added, so as to determine how quicklythe biofilm was able to regrow to its pretreatment size.

The compounds, compositions, methods, and processes of the inventionwill be better understood by reference to the following examples, whichare intended as an illustration of and not a limitation upon the scopeof the invention.

5. EXAMPLES

The foregoing can be better understood by reference to the followingexamples, which are presented for purposes of illustration and are notintended to limit the scope of the invention.

Imidazolines can be prepared as described in Examples 1-5, and asdescribed in U.S. Pat. Nos. 6,488,868, 7,057,050, and 7,951,754, thecontents of which are hereby incorporated by reference in theirentirety. Imidazolines can also be commercially available.

Example 1

To prepare the imidazoline above wherein R² is —C₁₇H₃₅, —C₁₇H₃₃, or—C₁₇H₃₁, sixty grams of Tall Oil Fatty Acid (TOFA) was placed in a 250ml, 4-neck flask equipped with an overhead stirrer, thermocouple,addition funnel and a Dean-Stark trap. The TOFA was heated to 60° C. andthen 25 grams of N-propyl-ethylenediamine was added dropwise rapidly.The resulting mixture turned from light yellow to dark red andexothermed to 100° C. The mixture was then heated to 120-140° C. for 3hours. The hydrocarbon collected in the trap was returned to the flask.The mixture was thereafter heated to 160° C. for 1 hour while allowingwater to collect in the Dean-Stark trap.

The resulting mixture was then heated at 165° C. for 2 hours and then at225° C. for an additional hour during which time any further evolvedwater was collected. A nitrogen sweep was applied and the speed of theoverhead stirrer was increased to facilitate removal of water. Followingfurther heating of the mixture to 225° C. for an additional 1.5 hours,the reaction mixture was cooled and 65.9 grams of the resultingimidazoline mixture was then reacted with 18.7 grams of acrylic acidwhich was carefully added dropwise to the imidazoline product. Atemperature rise of about 70-89° C. was observed. After exotherm hadceased, the reaction temperature was raised to about 100° C. for 2hours. The resulting N-propyl-2-heptadecenyl imidazoline acrylate wasrecovered.

Example 2

To prepare the imidazoline above wherein R² is —C₁₇H₃₅, —C₁₇H₃₃ or—C₁₇H₃₁, sixty grams of Tall Oil Fatty Acid (TOFA) was placed in a 250ml, 4-neck flask equipped with an overhead stirrer, thermocouple,addition funnel and a Dean-Stark trap. The TOFA was heated to 60° C. andthen 28.5 grams (0.245 mol) of N-butylethylenediamine was added dropwiserapidly. The resulting mixture turned from light yellow to dark red andexothermed to 84° C. The mixture was then heated to 160° C. for 3.5hours until no further water evolved. The hydrocarbon collected in thetrap was returned to the flask. The mixture was thereafter heated to160° C. for 1 hour while allowing water to collect in the Dean-Starktrap.

Fifty grams (0.132 mole) of the resulting mixture was then heated at225° C. for an additional hour during which time any further evolvedwater was collected. A nitrogen sweep was applied and the speed of theoverhead stirrer was increased to facilitate removal of water. Followingfurther heating of the mixture to 225° C. for an additional 1.5 hours,the reaction mixture was cooled and 45.25 grams of the resultingimidazoline mixture was then reacted with 10.4 grams of acrylic acidwhich was carefully added dropwise to the imidazoline product. Atemperature rise to about 88° C. was observed. After exotherm hadceased, the reaction temperature was raised to about 120° C. for 2hours. The resulting N-butyl-2-heptadecenyl imidazoline acrylate wasrecovered.

Example 3

To prepare the imidazoline above wherein R² is —C₁₇H₃₅, —C₁₇H₃₃ or—C₁₇H₃₁, sixty grams of Tall Oil Fatty Acid (TOFA) was placed in a 250ml, 4-neck flask equipped with an overhead stirrer, thermocouple,addition funnel and a Dean-Stark trap. The TOFA was heated to 60° C. and35.3 grams (0.265 mol) of N-hexylethylenediamine was added dropwiserapidly. The resulting mixture turned from light yellow to dark red andexothermed to 87° C. The mixture was heated to 160° C. for 3.5 hoursuntil no further water evolved. The hydrocarbon collected in the trapwas returned to the flask. The mixture was thereafter heated at 160° C.for 1 hour while allowing water to collect in the Dean-Stark trap.

Sixty one grams of the resulting mixture was then heated at 225-230° C.for an hour and then at 225° C. for an additional hour during which timeany further evolved water was collected. A nitrogen sweep was appliedand the speed of the overhead stirrer was increased to facilitateremoval of water. Following further heating of the mixture to 225° C.for an additional 1.5 hours, the reaction mixture was cooled and 55.93grams of the resulting imidazoline mixture was then reacted in a 3-neck250 ml flask with 18.7 grams of acrylic acid which was carefully addeddropwise to the imidazoline product. A temperature rise to about 92° C.was observed. After exotherm had ceased, the reaction temperature wasraised to about 120° C. for 2 hours. The resultingN-hexyl-2-heptadecenyl imidazoline acrylate was recovered.

Example 4

To prepare the imidazoline compound above wherein R² and R¹⁴ areindependently —C₁₇H₃₅, —C₁₇H₃₃ or —C₁₇H₃₁, 220.4 grams (0.78 moles) of atall oil fatty acid mixture (“TOFA”-comprised of about 46% oleic acid,about 41% linoleic acid, about 4% stearic acid, and about 9% otheracids) was weighed and placed into a 500 ml round bottom, four-neckflask equipped with an overhead stirrer, thermocouple, addition funnel,and Dean-Stark trap.

The TOFA was heated to about 70° C. and 38.8 grams (0.38 moles) ofdiethylenetriamine was added dropwise, with stirring. An exotherm ofabout 35° C. was observed. The mixture was further heated at 130° C. for1 hour and at 160° C. for 2 hours. The mixture was then held at 250° C.for 2 hours with a nitrogen gas sweep. 17.6 ml (about 86% theoreticalamount of water for 100% imidazoline formation) of water was collected.The mixture was cooled and 60.8 grams (0.84 moles) of glacial acrylicacid was added dropwise, with stirring, which had an exotherm between 47and 67° C. This final mixture was heated at 120 to 125° C. for 2 hoursto ensure complete reaction.

Example 5

To prepare the imidazoline above wherein R² is —C₁₇H₃₅, —C₁₇H₃₃ or—C₁₇H₃₁, 175 g (0.62 mol) of TOFA was placed in a 500 mL round bottomfour-neck flask equipped with an overhead stirrer, addition funnel,thermocouple and Dean-Stark trap. The acid was heated to 60° C. and asweep of nitrogen gas was maintained over the surface of the liquidthroughout the reaction. When the temperature reached 60° C., 82 g (0.8mol) of DETA was added dropwise rapidly. An exotherm of about 40° C. wasobserved. The mixture was heated to 175° C. with stirring until thetheoretical amount of water for amide formation (11 g) was collected.The infrared spectrum of the mixture at this point indicated thepresence of amide (absorption at about 1630 and 1550 cm⁻¹) and free N—H(absorption at about 3315 cm⁻¹). The temperature was increased to 225°C. and maintained there for 2 hours (84% of the theoretical amount ofwater for 100% imidazoline formation was collected). The infraredspectrum exhibited the same two broad bands noted above and a sharper,intense band between them around 1610 cm⁻¹, indicative of imidazoline.

69.8 g (0.2 mol, presuming the composite molecular weight of the amineimidazoline is 349 g/mole) of the resultant amine imidazoline mixturewas weighed into a 250 mL round bottom four-neck flask equipped with anoverhead stirrer, addition funnel and thermocouple. To this was added43.2 g (0.6 mol) acrylic acid via the addition funnel. The exotherm wasnoted and the mixture heated at 120° C. for 2 hours.

Biocide Testing

Evaluation of the biocide compositions disclosed herein was performedthrough a dynamic flow loop test where both planktonic and sessileorganisms could be monitored. To start this testing, fluid from thefield, as well as cultured organisms from the field, were placed intothe system and allowed to grow for approximately 7 weeks, providing amature biofilm that can then be challenged by the biocide treatment.

The test system holds approximately 1.5 liters of fluid that arecontinually circulated over 1018 carbon steel biostuds located in the 6o'clock position of a modified Robbin's device. The device holds amaximum of eight biostuds in the 6 o'clock position. The productionfluid was pumped through the system at a rate of approximately 3.1gallons per minute, which allows for deposition of microorganisms andsolids onto the biostuds. The health of the microbial population wasmonitored weekly during the biofilm growth period using ATPquantification.

After concluding the establishment of a mature biofilm, the sessile killstudy was initiated. During the study, solid and fluid samples werecollected before and after the biocide treatment at scheduled intervals.The following chemicals were tested in the system: (study 1) THPS wastested against THPS/quat #2, (study 2) THPS/quat #1, and (study 3)THPS/quat/imidazoline. A baseline reading was taken, during all of thestudies, prior to the addition of the chemical to the individual flowloop. This consisted of a fluid sample as well as two biostuds. Afterremoval of the baseline sample, either (study 1) THPS or THPS/quat #2,(study 2) THPS/quat #1, (study 3) THPS/quat/imidazoline was added to aflow loop at the predetermine concentration with a 4 hour contact time.After the 4 hour treatment, a second fluid sample and two coupons wereremoved from each flow loop. The total fluid in each flow loop was thenremoved from the system and untreated production fluid added back tomimic a batch biocide treatment followed by continued production.Additional biostuds were removed at 24, 48 and either 72 or 120-hoursafter the new fluid was added to determine how quickly the biofilm wasable to regrow to its pretreatment size.

One of the features of this chemistry is the enhanced biofilm kill thata formulation has when the imidazoline is present even though theimidazoline itself has no enhanced kill on planktonic organisms. FIG. 1shows a planktonic biocide efficacy kill study where varying amounts ofimidazoline were mixed with a biocidal quaternary. As the amount of theimidazoline was increased, the microbial kill decreased, as shows inFIG. 1.

FIG. 2 is a compilation of three separate experiments illustrating theability to kill microbes present in a biofilm by using THPS alone, THPSin combination with one of two different quats, or THPS with a quat plusthe acrylated imidazoline. The initial data point before treatment isset to 100% and all other readings are reported as a percent changecompared to the baseline. THPS alone provides initial biofilm kill, butthe biofilm is larger than it was before treatment within 24 hours. THPSplus the quats provided enhanced control with quat #2 compared to THPSalone but no enhanced control with quat #1. Quat #2 was N,N-dimethyl,N-alkyl-benzylammonium chloride wherein the alkyl was a mixture of C₁₂,C₁₄, and C₁₆ alkyl groups. The imidazoline used was availablecommercially under the tradename Clean N Cor from Nalco. TheTHPS/quat/imidazoline provided a synergistic effect where biofilm growthwas reduced to less than 0.3% of the initial size and maintained for atleast 120 hours when the testing was stopped.

Planktonic kill in the dynamic flow loops was also evaluated immediatelyafter a 4 hour contact time with the biocide. The results of thattesting are shown in Table 1. Compared to THPS alone, the addition of aquat does provide some enhanced kill. The addition of a quat plus theimidazoline to THPS provided a synergistic effect where the planktonickill was significantly enhanced compared to THPS or THPS plus quat only.

TABLE 1 Planktonic kill data % Biocide Dosage reduction THPS 112.5 ppmactive THPS 81.8% THPS/quat #1 140 ppm active THPS 94.4% THPS/quat#252.5 ppm active THPS 83.2% THPS/quat#2 140 ppm active THPS 91.0%THPS/quat/imidazoline 47.5 ppm active THPS 99.8% quat #1 =benzyl-(C₁₂-C₁₆ linear alkyl)-dimethyl-ammonium chloride quat #2 = samequat from the THPS/quat/imidazoline blend (without the imidazole)

Based on these results, a planktonic kill study, as described above, anda static sessile kill study were employed to determine the ratio of theTHPS/quat/imidazoline that yields the most synergistic effect. Theresults indicated that the formulations titled N-HF #2 and N-HF #3provided the best overall kill for both the planktonic and staticsessile tests, as shown in FIG. 3. N-HF #2 contained 45 wt. % Clean NCor and N-HF #3 contained 40 wt. % Clean N Cor.c

Additional formulations were prepared with an emulsion breaker toenhance oil/water separation when using the synergistic biocideformulations. For this test, synthetic brine and crude from the fieldwere added to a 250 mL flask. After the addition of the designatedchemistry, the flask was mixed for 30 seconds at 2000 rpm. Once themixing was completed, the height of each layer was recorded after 5, 20,and 60 minutes.

FIG. 4 shows the blank, or negative control, against the synergisticbiocide formulation without the emulsion breaker and the synergisticbiocide formulation with the emulsion breaker at concentrations of 100ppm, 500 ppm, and 1000 ppm, after 20 minutes. Observations revealed thecrude emulsion seems to be tighter with the formulation including theemulsion breaker than formulation without the emulsion breaker. Thisprovides an additional benefit to the biocide formulations.

After determining the ratio that yields the most synergistic effects andthe addition of the emulsion breaker, an exemplary biocide formulationaccording to Table 2 was prepared. A sessile kill study was conducted todetermine the efficacy of the formulation of Table 2. This test revealeda 98.6% reduction in the planktonic community and a 95.2% reduction inthe sessile community after a 4 hour contact time.

TABLE 2 Component (wt %) Imidazoline imidazoline(s) of formula (I): 11

(I) wherein R¹ is substituted alkyl; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁;R³ is —CH₂CH₂CO₂ ⁻; R⁴ is H; and R⁵ is H Quaternary benzalkonium saltsof the formula: 20.5 Amine

wherein n is 12, 14, 16, and/or 18; and X is Cl Phosphoniumtetrakis(hydroxymethyl)phosphonium 7.5 Salt sulphate (THPS):

Demulsifier acrylic acid, polymer with t-butylphenol, 2.6 formaldehyde,maleic anhydride, propylene oxide, and ethylene oxide (CAS RegistryNumber: 178603-70-8) Synergist 2-mercaptoethanol 3.5 Alcoholicmethanol/isopropanol 40 Solvent Aqueous Water 14.9 Solvent

Example 6

A study was conducted to assess the corrosiveness of the biocide and twoother commonly used biocide products. In this evaluation the corrosionrates of C1018 carbon steel in CO₂ saturated brine at 100% water cutwere monitored in the presence of various biocides at concentrations ofup to 5,000 ppm using the wheel box corrosion test at 80° C. The resultsfor the three biocide types, V08, 75% THPS, and 50% glutaraldehyde, areprovided in FIG. 5 (A-C). All samples were run in triplicate. The blankor baseline corrosion rate in the 24 hour wheel box test provided anaverage corrosion rate of 58.60 mpy (mils penetration per year) whilethe 75% THPS and 50% glutaraldehyde biocides resulted in corrosion ratesof 53.78 and 30.07 mpy, respectively. Similar trends emerged for THPSand glutaraldehyde as the concentration of each increased. However, V08yielded a corrosion rate of 5.14 mpy at 100 ppm. The data indicated thatthe concentration of V08 is inversely proportional to the corrosionrate. The V08 product included water, 2-ethylhexanol, iso-propylalcohol, Clean N Cor from Nalco, THPS, and acrylic acid, polymer witht-butylphenol, formaldehyde, maleic anhydride, propylene oxide, andethylene oxide (CAS Registry Number: 178603-70-8). Overall the datarevealed that V08 can provide corrosion protection.

Any ranges given either in absolute terms or in approximate terms areintended to encompass both, and any definitions used herein are intendedto be clarifying and not limiting. Notwithstanding that the numericalranges and parameters setting forth the broad scope of the invention areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.Moreover, all ranges disclosed herein are to be understood to encompassany and all subranges (including all fractional and whole values)subsumed therein.

Furthermore, the invention encompasses any and all possible combinationsof some or all of the various embodiments described herein. Any and allpatents, patent applications, scientific papers, and other referencescited in this application, as well as any references cited therein, arehereby incorporated by reference in their entirety.

What is claimed is:
 1. A method of controlling microbe proliferation ina system used in a coal-fired process, a waste-water process, a farm, aslaughter house, a land-fill, a municipality waste-water plant, a cokingcoal process, or a biofuel process, the method comprising contacting thesystem with an effective amount of a biocide composition, the biocidecomposition comprising an imidazoline compound; a quaternary amine; anda phosphonium compound; wherein the imidazoline compound has a structureof formula (I), (II), or (III),

wherein R¹, R⁴, and R⁵ are each independently selected from hydrogen,alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, andheterocycle, said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,aryl, heteroaryl, and heterocycle each independently, at eachoccurrence, unsubstituted or substituted with 1 to 3 substituentsindependently selected from halogen, —COR⁶, —CO₂R⁷, —SO₃R⁸,—PO₃H₂,)—CON(R⁹)(R¹⁰), —OR¹¹, and —N(R¹²)(R¹³); R² is a radical derivedfrom a fatty acid; R³ and R^(x) are independently selected from aradical derived from an unsaturated acid; R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹are each independently, at each occurrence, selected from hydrogen,alkyl, and alkenyl; R¹² and R¹³ are each independently, at eachoccurrence, selected from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵,-alkyl-COR¹⁶, and -alkyl-CO₂R¹⁷; and R¹⁴,R¹⁵, R¹⁶, and R¹⁷ are eachindependently, at each occurrence, selected from hydrogen, alkyl, andalkenyl.
 2. The method of claim 1, wherein the imidazoline compound hasformula (I),

wherein R¹, R⁴, and R⁵ are each independently selected from hydrogen,alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, andheterocycle, said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,aryl, heteroaryl, and heterocycle each independently, at eachoccurrence, unsubstituted or substituted with 1 to 3 substituentsindependently selected from halogen, -COR⁶, —CO₂R⁷, —SO₃R⁸, —PO₃H₂,—CON(R⁹)(R¹⁰) —OR¹¹, and —N(R¹²)(R¹³); R² is a radical derived from afatty acid; R³ is selected from a radical derived from an unsaturatedacid; R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently, at eachoccurrence, selected from hydrogen, alkyl, and alkenyl; R¹² and R¹³ areeach independently, at each occurrence, selected from hydrogen, alkyl,—COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and -alkyl-CO₂R¹⁷; and R¹⁴, R¹⁵, R¹⁶, andR¹⁷ are each independently, at each occurrence, selected from hydrogen,alkyl, and alkenyl.
 3. The method of claim 2, wherein R¹ isunsubstituted C₂-C₆-alkyl; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen, C₁-C₆-alkyl, or R^(e) isabsent; R⁴ is hydrogen; and R⁵ is hydrogen.
 4. The method of claim 2,wherein R¹ is linear C₂-alkyl, substituted with one substituent that isa terminal —N(R¹²)(R¹³), wherein R¹² is hydrogen and R¹³ is —COR¹⁴,wherein R¹⁴ is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R² is —C₁₇H₃₅, —C₁₇H₃₃, or—C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen, C₁-C₆-alkyl,or R^(e) is absent; R⁴ is hydrogen; and R⁵ is hydrogen.
 5. The method ofclaim 2, wherein R¹ is linear C₂-alkyl, substituted with one substituentthat is a terminal —N(R¹²)(R¹³), wherein R¹² and R¹³ are each a—C₂-alkyl-CO₂R¹⁷, wherein R¹⁷ is hydrogen or R¹⁷ is absent; R² is—C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) ishydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ is hydrogen; and R⁵ ishydrogen.
 6. The method of claim 1, wherein the imidazoline compound hasformula (II),

wherein R¹, R⁴, and R⁵ are each independently selected from hydrogen,alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, andheterocycle, said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,aryl, heteroaryl, and heterocycle each independently, at eachoccurrence, unsubstituted or substituted with 1 to 3 substituentsindependently selected from halogen, —COR⁶, —CO₂R⁷, —SO₃R⁸,—PO₃H₂,)—CON(R⁹)(R¹⁰), —OR¹¹, and —N(R¹²)(R¹³); R² is a radical derivedfrom a fatty acid; R³ and R^(x) are each independently selected from aradical derived from an unsaturated acid; R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹are each independently, at each occurrence, selected from hydrogen,alkyl, and alkenyl; R¹² and R¹³ are each independently, at eachoccurrence, selected from hydrogen, alkyl, —COR¹⁴, —CO₂R¹⁵,-alkyl-COR¹⁶, and -alkyl-CO₂R¹⁷; and R¹⁴, R¹⁵, R¹⁶, and R¹⁷ are eachindependently, at each occurrence, selected from hydrogen, alkyl, andalkenyl.
 7. The method of claim 6, wherein R¹ is unsubstitutedC₂-C₆-alkyl; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e),wherein R^(e) is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R^(x) is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen, C₁-C₆-alkyl, or R^(e) isabsent; R⁴ is hydrogen; and R⁵ is hydrogen.
 8. The method of claim 6,wherein R¹ is linear C₂-alkyl, substituted with one substituent that isa terminal —N(R¹²)(R¹³), wherein R¹² is hydrogen and R¹³ is —COR¹⁴,wherein R¹⁴ is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R² is —C_(i7)H₃₅, —C₁₇H₃₃,or —C₁₇H₃₁; R³ is —CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen,C₁-C₆-alkyl, or R^(e) is absent; R^(x) is —CH₂CH₂CO₂R^(e), wherein R^(e)is hydrogen, C₁-C₆-alkyl, or R^(e) is absent; R⁴ is hydrogen; and R⁵ ishydrogen.
 9. The method of claim 6, wherein R¹ is linear C₂-alkyl,substituted with one substituent that is a terminal —N(R¹²)(R¹³),wherein R¹² and R¹³ are each a —C₂-alkyl-CO₂R¹⁷, wherein R¹⁷ is hydrogenor R¹⁷ is absent; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R³ is—CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen, C₁-C₆-alkyl, or R^(e) isabsent; R^(x) is —CH₂CH₂CO₂R^(e), wherein R^(e) is hydrogen,C₁-C₆-alkyl, or R^(e) is absent; R⁴ is hydrogen; and R⁵ is hydrogen. 10.The method of claim 1, wherein the imidazoline compound has formula(III),

wherein R¹, R⁴, and R⁵ are each independently selected from hydrogen,alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, andheterocycle, said alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,aryl, heteroaryl, and heterocycle each independently, at eachoccurrence, unsubstituted or substituted with 1 to 3 substituentsindependently selected from halogen, —COR⁶, —CO₂R⁷, —SO₃R⁸, —PO₃H₂,—CON(R⁹)(R¹⁰), and —N(R¹²)(R¹³); R² is a radical derived from a fattyacid; R⁶, R⁷, R⁸, R⁹, and R¹⁰are each independently, at each occurrence,selected from hydrogen, alkyl, and alkenyl; R¹² and R¹³ are eachindependently, at each occurrence, selected from hydrogen, alkyl,—COR¹⁴, —CO₂R¹⁵, -alkyl-COR¹⁶, and -alkyl-CO₂R¹⁷; and R¹⁴, R¹⁵, R¹⁶andR¹⁷ are each independently, at each occurrence, selected from hydrogen,alkyl, and alkenyl.
 11. The method of claim 10, wherein R¹ isunsubstituted C₂-C₆-alkyl; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ ishydrogen; and R⁵ is hydrogen.
 12. The method of claim 10, wherein R¹ islinear C₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² is hydrogen and R¹³ is —COR¹⁴, wherein R¹⁴ is—C₁₇H₃₅, —C₁₇H₃₃, —C₁₇H₃₁; R² is —C₁₇H₃₅, —C₁₇H₃₃, or —C₁₇H₃₁; R⁴ ishydrogen; and R⁵ is hydrogen.
 13. The method of claim 10, wherein R¹ islinear C₂-alkyl, substituted with one substituent that is a terminal—N(R¹²)(R¹³), wherein R¹² and R¹³ are each a —C₂-alkyl-CO₂R¹⁷, whereinR¹⁷ is hydrogen or R¹⁷ is absent; R² is —C₁₇H₃₅, —C ₁₇H₃₃, or —C₁₇H₃₁;R⁴ is hydrogen; and R⁵ is hydrogen.
 14. The method of claim 1, whereinthe quaternary amine has the formula[N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X] wherein R^(5a), R^(6a), R^(7a), andR^(8a) are each independently selected from substituted or unsubstitutedC₁-C₁₈-alkyl; and X is Cl, Br or I.
 15. The method of claim 14, whereinR^(5a), R^(6a), R^(7a), and R^(8a) are each independently selected fromthe group consisting of unsubstituted C₁-C₁₈-alkyl, C₁-C₁₈-hydroxyalkyl,and benzyl.
 16. The method of claim 1, wherein the quaternary amine isselected from the group consisting of tetramethyl ammonium chloride,tetraethyl ammonium chloride, tetrapropyl ammonium chloride, tetrabutylammonium chloride, tetrahexyl ammonium chloride, tetraoctyl ammoniumchloride, benzyltrimethyl ammonium chloride, benzyltriethyl ammoniumchloride, phenyltrimethyl ammonium chloride, phenyltriethyl ammoniumchloride, cetyl benzyldimethyl ammonium chloride, hexadecyl trimethylammonium chloride, dimethyl C₁₂-₁₆-alkyl benzyl ammonium chloride,monomethyl di-C₁₂-₁₆-alkyl benzyl quaternary ammonium chloride, benzyltriethanolamine quaternary ammonium chloride, benzyldimethylaminoethanolamine quaternary ammonium chloride, cocoalkyldimethyl benzyl ammonium chloride, and combinations thereof.
 17. Themethod of claim 1, wherein the phosphonium compound is selected from thegroup consisting of alkyltris(hydroxyorgano)phosphonium salts,alkenyltri s(hydroxyorgano)phosphonium salts,tetrakis(hydroxyorgano)phosphonium salts, and combinations thereof. 18.The method of claim 17, wherein the phosphonium compound is selectedfrom the group consisting of C₁-C₃-alkyltris(hydroxymethyl)phosphoniumsalts, C₂-C₃-alkenyltris(hydroxymethyl)phosphonium salts,tetrakis(hydroxymethyl)phosphonium salts, and combinations thereof. 19.The method of claim 18, wherein the phosphonium compound is selectedfrom the group consisting of tetrakis(hydroxymethyl)phosphonium sulphate(THPS), tetrakis(hydroxymethyl)phosphonium chloride,tetrakis(hydroxymethyl)phosphonium phosphate,tetrakis(hydroxymethyl)phosphonium formate,tetrakis(hydroxymethyl)phosphonium acetate,tetrakis(hydroxymethyl)phosphonium oxalate, and combinations thereof.20. The method of claim 1, further comprising a demulsifier, and thedemulsifier is selected from the group consisting ofdodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonicacid (NAXSA), epoxylated and propoxylated compounds, anionic cationicand nonionic surfactants, and resins, phenolic and epoxide resins, andcombinations thereof.